Ultrathin Ionic Diodes with Electrostatically Heterogeneous Hybrid Interfaces of Nanoporous SiO2 Nanofilms and Polymer Layer-by-Layer Multilayers.

Nanofluidic ionic diodes have attracted much attention due to their unique functions as unidirectional ion transportation ability and promising applications from molecular sensing, and energy harvesting to emerging neuromorphic devices. However, it remains a challenge to fabricate diode-like nanofluidic systems with ultrathin film thickness <100 nm. Herein the formation of ultrathin ionic diodes from hybrid nanoassemblies of nanoporous (NP) SiO2 nanofilms and polyelectrolyte layer-by-layer (LbL) multilayers is described. Ultrathin ionic diodes are prepared by integrating polyelectrolyte multilayers onto photo-oxidized NP SiO2 nanofilms obtained from silsesquioxane-containing block copolymer thin films as a template. The obtained ultrathin ionic diodes exhibit ion current rectification (ICR) properties with high ICR factor = ≈20 under low ionic strength and asymmetric pH conditions. It is concluded that this ICR behavior arises from effective ion accumulation and depletion at the interface of NP SiO2 nanofilms and LbL multilayers attributed to high ion selectivity by combining the experimental data and theoretical calculations using finite element methods. These results demonstrate that the hybrid nano assemblies of NP SiO2 nanofilms and polyelectrolyte LbL multilayers have potential applications for (bio)sensing materials and integrated ionic circuits for seamless connection of human-machine interfaces.

Recent Biomedical Applications of Functional Materials Based on Polyhedral Oligomeric Silsesquioxane (POSS).

Polyhedral oligomeric silsesquioxane (POSS) is a 3D, cage-like nanoparticle with an inorganic Si-O-Si core and eight tunable corner functional groups. Its well-defined structure grants it distinctive physical, chemical, and biological properties and has been widely used for preparing high-performance materials. Recently, click chemistry has enabled the synthesis of various functional POSS-based materials for diverse biomedical applications. This article reviews the recent applications of POSS-based materials in the biomedical field, including cancer treatment, tissue engineering, antibacterial use, and biomedical imaging. Representative examples are discussed in detail. Among the various POSS-based applications, cancer treatment and tissue engineering are the most important. Finally, this review presents the current limitations of POSS-based materials and provides guidance for future research.

A strategy to fabricate nanostructures with sub-nanometer line edge roughness.

Line edge roughness (LER) has been an important issue in the nanofabrication research, especially in integrated circuits. Despite numerous research studies has made efforts on achieving smaller LER value, a strategy to achieve sub-nanometer level LER still remains challenging due to inability to deposit energy with a profile of sub-nanometer LER. In this work, we introduce a strategy to fabricate structures with sub-nanometer LER, specifically, we use scanning helium ion beam to expose hydrogen silsesquioxane (HSQ) resist on thin SiNx membrane (∼20 nm) and present the 0.16 nm spatial imaging resolution based on this suspended membrane geometric construction, which is characterized by scanning transmission electron microscope (STEM). The suspended membrane serves as an energy filter of helium ion beam and due to the elimination of backscattering induced secondary electrons, we can systematically study the factors that influences the LER of the fabricated nanostructures. Furthermore, we explore the parameters including step size, designed exposure linewidth (DEL), delivered dosage and resist thickness and choosing the high contrast developer, the process window allows to fabricate lines with 0.2 nm LER is determined. AFM measurement and simulation work further reveal that at specific beam step size and DEL, the nanostructures with minimum LER can only be fabricated at specific resist thickness and dosage.

Biosensor for ATP detection via aptamer-modified PDA@POSS nanoparticles synthesized in a microfluidic reactor.

This study introduces aptamer-functionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticles for adenosine triphosphate (ATP) detection where the POSS nanoparticles were synthesized in a one-step, continuous flow microfluidic reactor utilizing thermal polymerization. A microemulsion containing POSS monomers was generated in the microfluidic reactor which was designed to prevent clogging by using a continuous oil flow around the emulsion during thermal polymerization. Surfaces of POSS nanoparticles were biomimetically modified by polydopamine. The aptamer sequence for ATP was successfully attached to POSS nanoparticles. The aptamer-modified POSS nanoparticles were tested for affinity-based biosensor applications using ATP as a model molecule. The nanoparticles were able to capture ATP molecules successfully with an affinity constant of 46.5 [Formula: see text]M. Based on this result, it was shown, for the first time, that microfluidic synthesis of POSS nanoparticles can be utilized in designing aptamer-functionalized nanosystems for biosensor applications. The integration of POSS in biosensing technologies not only exemplifies the versatility and efficacy of these nanoparticles but also marks a significant contribution to the field of biorecognition and sample preparation.

Polyhedral Oligomeric Silsesquioxane-Based Nanoparticles for Efficient Chemotherapy of Glioblastoma.

Glioblastoma (GBM) is the most common lethal brain tumor with dismal treatment outcomes and poor response to chemotherapy. As the regulatory center of cytogenetics and metabolism, most tumor chemotherapeutic molecules exert therapeutic effects in the nucleus. Nanodrugs showing the nuclear aggregation effect are expected to eliminate and fundamentally suppress tumor cells. In this study, a nanodrug delivery system based on polyhedral oligomeric silsesquioxane (POSS) is introduced to deliver drugs into the nuclei of GBM cells, effectively enhancing the therapeutic efficacy of chemotherapy. The nanoparticles are modified with folic acid and iRGD peptides molecules to improve their tumor cell targeting and uptake via receptor-mediated endocytosis. Nuclear aggregation allows for the direct delivery of chemotherapeutic drug temozolomide (TMZ) to the tumor cell nuclei, resulting in more significant DNA damage and inhibition of tumor cell proliferation. Herein, TMZ-loaded POSS nanoparticles can significantly improve the survival of GBM-bearing mice. Therefore, the modified POSS nanoparticles may serve as a promising drug-loaded delivery platform to improve chemotherapy outcomes in GBM patients.

Ionic Liquids Containing Silsesquioxane and Cyclic Siloxane Frameworks.

This paper describes the author's recent work on the preparation and properties of thermally stable ionic liquids (ILs) containing siloxane frameworks. Quaternary ammonium and imidazolium salt-type ILs containing random oligosilsesquioxane frameworks were successfully prepared via the hydrolytic condensation of the corresponding organotrialkoxysilanes by using an aqueous superacid bis(trifluoromethanesulfonyl)imide (HNTf2 ) solution as a catalyst and solvent. Imidazolium salt-type ILs containing polyhedral oligomeric silsesquioxane (POSS) frameworks were also prepared through a reaction similar to that described above by using a water/methanol mixed solution of HNTf2 . In addition, amorphous POSSs with two types of ionic groups randomly distributed in the side chain were prepared. These POSSs were ILs exhibiting fluidity at relatively low temperatures. Furthermore, imidazolium and ammonium salt-type ILs containing cyclic oligosiloxane frameworks were prepared through a reaction similar to that of the corresponding organodialkoxysilanes. The thermal decomposition temperatures of the above ILs containing siloxane frameworks were higher than those of general ILs.

Dual-mode colorimetric/fluorescent chemosensor for Cu2+/Zn2+ and fingerprint imaging based on rhodamine ethylenediamine bis(triazolyl silsesquioxane).

A novel dual functional and visual rhodamine ethylenediamine bis(triazolyl silsesquioxane) (RBS) chemosensor was successfully synthesized using "click" chemistry. The results have unambiguously demonstrated that RBS can act in fluorescent and colorimetric sensing of Cu2+ and Zn2+ by their respective coordination with triazole structures and, more importantly, it has also been found that triazole-amide of RBS could turn on chelation-enhanced fluorescence (CHEF) of Cu2+. Remarkably, the addition of Cu2+ triggered an enhanced fluorescent emission by 63.3-fold (ϕF = 0.41), while Zn2+ enhanced it 48.3-fold (ϕF = 0.29) relative to the original RBS (ϕF = 0.006) in acetonitrile (MeCN) solvent. The fluorescent limit of detection for Cu2+ and Zn2+ is similar and fall within 3.0 nM, while under colorimetric sensing the responses were 2.14 × 10-8 and 4.0 × 10-8 mol L-1, respectively. Moreover, the effective sensing profile of RBS and extended applications of RBS-Cu2+ and RBS-Zn2+ for fingerprinting detection and imaging were observed with adequate sensitivity, stability and legibility under the dual visual responses.

Regioisomeric Giant Triblock Molecules: Role of the Linker.

In this study, polyhedral oligomeric silsesquioxane (POSS) based giant triblock molecules with precisely defined regio-configuration are modularly prepared through highly efficient coupling reactions. The length of the linker connecting neighboring nanoparticles is elaborately designed to regulate the geometric constraints. The triblock molecules adopt a folded packing during phase separation, and the regio-configuration imparts direct influence on the self-assembly behaviors. The ortho-isomers form periodic structures with a larger domain size, larger interfacial curvature, and enhanced phase stability. The regio-effect is closely related to the length and symmetry of the linker. As the linker extends, the neighboring particles gradually decouple, and the regio-effect diminishes. The symmetry of the linker shows an even more profound impact. This work quantitatively scrutinized the role of the linker, opening an avenue for engineering the assembled structures with molecular precision.

Efficient Adsorption and Extraction of Glutathione S-Transferases with Glutathione-Functionalized Graphene Oxide-Polyhedral Oligomeric Silsesquioxane Composite.

Glutathione S-transferases (GSTs) are important type-II detoxification enzymes that protect DNA and proteins from damage and are often used as protein tags for the expression of fusion proteins. In the present work, octa-aminopropyl caged polyhedral oligomeric silsesquioxane (OA-POSS) was prepared via acid-catalyzed hydrolysis of 3-aminopropyltriethoxysilane and polymerized on the surface of graphene oxide (GO) through an amidation reaction. Glutathione (GSH) was then modified to GO-POSS through a Michael addition reaction to obtain a GSH-functionalized GO-POSS composite (GPG). The structure and characteristics of the as-prepared GPG composite were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermogravity analysis, and surface charge analysis. The specific binding interactions between glutathione and GST gave GPG favorable adsorption selectivity towards GST, and other proteins did not affect GST adsorption. The adsorption behavior of GST on the GPG composite conformed to the Langmuir isotherm model, and the adsorption capacity of GST was high up to 364.94 mg g-1 under optimal conditions. The GPG-based solid-phase adsorption process was applied to the extraction of GST from a crude enzyme solution of pig liver, and high-purity GST was obtained via SDS-PAGE identification.

Fabrication of monolithic capillary columns with inner diameter 50-530 µm employing a mixture of pentaerythritol tetraacrylate and polyhedral oligomeric silsesquioxane-methacrylate as crosslinkers.

Highly crosslinked monolithic capillary columns with inner diameters in the range of 50-530 µm were prepared by radical polymerization of pentaerythritol tetraacrylate, polyhedral oligomeric silsesquioxane-methacrylate, and n-octadecyl methacrylate in the presence of methanol, dodecyl alcohol, and polyethylene glycol lauryl ether. Columns were evaluated by inverse size-exclusion chromatography employing a set of polystyrene standards of narrow molecular-size distribution and by scanning electron microscopy. Chromatographic performance under reversed-phase conditions was also evaluated. The combination of two effective crosslinkers as pentaerythritol tetraacrylate and polyhedral oligomeric silsesquioxane-methacrylate in the polymerization mixture allows for the preparation of robust and efficient monolithic capillary columns within a fairly wide range of internal diameters.

POSS-based fluorescence sensor for rapid analysis of ß-carotene in health products.

In recent years, fluorescent organic-inorganic hybrid nanomaterials have received much interest as potential fluorescent sensor materials. In this study, fluorescent organic-inorganic hybrid nanomaterials (POSS@ANT) were created using polyhedral oligomeric silsesquioxane as the precursor and 9,10-bromoanthracene as the monomer. The morphology and composition of POSS@ANT, as well as its pore characteristics and fluorescence properties were studied. POSS@ANT displayed steady fluorescence emission at an excitation wavelength of 374 nm. Next, a ß-carotene fluorescence sensor was developed using the capacity of ß-carotene to quench the fluorescence of POSS@ANT. The quenching process is linked to acceptor electron transfer and energy transfer, and the sensor has a high selectivity for ß-carotene. This ß-carotene fluorescence analysis method that we established has a linear range of 0.2-4.3 mg/L and a detection limit of 0.081 mg/L. Finally, it was used to quantify ß-carotene in health products, the recovery rate was 91.1-109.9%, the relative standard deviation (RSD) was 2.2-4.3%, and the results were comparable with the results of high-performance liquid chromatography. The approach is reliable and can be used to determine ß-carotene in health products.

Thiolated Janus Silsesquioxane Tetrapod: New Precursors for Functional Materials.

Herein, we report synthetic strategies for the development of a bifunctional Janus T4 tetrapod (Janus ring), in which the orthogonal silsesquioxane and organic faces are independently functionalized. An all-cis T4 tetrasilanolate was functionalized to introduce thiol moieties on the silsesquioxane face and naphthyl groups on the organic face to introduce luminescent and self-organization properties. The stepwise synthesis conditions required to prepare such perfectly defined oligomers via a suite of well-defined intermediates and to avoid polymerization or reactions over all eight positions of the tetrapod are explored via 29Si, 13C and 1H NMR, FTIR and TOF-ESI mass spectroscopy. To the best of our knowledge, this is one of the few reports of Janus T4 tetrapods, with different functional groups located on both faces of the molecule, thus expanding the potential range of applications for these versatile precursors.

Design of Fluorescent Hybrid Materials Based on POSS for Sensing Applications.

Polyhedral oligomeric silsesquioxane (POSS) has a nanoscale silicon core and eight organic functional groups on the surface, with sizes from 0.7 to 1.5 nm. The three-dimensional nanostructures of POSS can be used to build all types of hybrid materials with specific performance and controllable nanostructures. The applications of POSS-based fluorescent materials have spread across various fields. In particular, the employment of POSS-based fluorescent materials in sensing application can achieve high sensitivity, selectivity, and stability. As a result, POSS-based fluorescent materials are attracting increasing attention due to their fascinating vistas, including unique structural features, easy fabrication, and tunable optical properties by molecular design. Here, we summarize the current available POSS-based fluorescent materials from design to sensing applications. In the design section, we introduce synthetic strategies and structures of the functionalized POSS-based fluorescent materials, as well as photophysical properties. In the application section, the typical POSS-based fluorescent materials used for the detection of various target objects are summarized with selected examples to elaborate on their wide applications.

Synthesis of Functionalized Silsesquioxane Nanomaterials by Rhodium-Catalyzed Carbene Insertion into Si-H Bonds.

We report carbene insertion into Si-H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si-H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki-Miyaura cross-coupling.

Interphase Building of Organic-Inorganic Hybrid Polymer Solid Electrolyte with Uniform Intermolecular Li+ Path for Stable Lithium Metal Batteries.

Lithium (Li) metal has been generally noticed as the most prospective anode for next-generation batteries attributed to its outstanding theoretical capacity and low electrochemical potential. Nevertheless, the unstable solid-electrolyte interphase (SEI) and uncontrollable dendrite growth cause poor reversibility and fetter the practical application of Li metal anodes. Herein, a new organic-inorganic hybrid polymer artificial SEI (POSS-LiBMAB) layer with uniform lithium-ion paths at a molecular level is designed to stabilize Li metal anodes. The SEI layer is constructed by the thiol-ene "click chemistry" reaction between inorganic polyhedral oligomeric silsesquioxane containing eight-mercaptopropyl (POSS-SH) with lithium bis (allylmalonato) borate (LiBMAB) on Li foil. What is more, the POSS-LiBMAB film can be cross-linked and self-reinforced via intermolecular SC bonds. Benefiting from its flexible polymeric covalent structure and noble inorganic Si8 O16 -type cubes, the organic-inorganic hybrid polymer layer is flexible and effectively tolerates the volume change of Li metal anodes during plating/stripping cycles. In addition, this layer shows loose and uniformly distributed electrostatic interaction between Li+ and charge delocalized sp3 boron-oxygen anions, which aids to form a uniform intermolecular Li+ path regulating the homogeneous distribution of Li+ flux on Li anodes. Finally, the designed POSS-LiBMAB layer has high ionic conductivity and lithium-ion transference number, which can effectively promote Li+ diffusion and guide Li deposition beneath the SEI layer. Therefore, with the protection of the POSS-LiBMAB layer, the Li metal anode exhibits stable cycling at 5 mA cm-2 for more than 1000 h, and the LFP//Li full cells also present outstanding cycling stability.

Constructing 3D Interconnected Si/SiOx /C Nanorings from Polyhedral Oligomeric Silsesquioxane.

Polyhedral oligomeric silsesquioxane (POSS) is a family of organic/inorganic hybrid materials with specific molecular symmetry, and shows great potential in the structural design of nanomaterials. Here, a "bottom-up" strategy is designed to fabricate 3D interconnected Si/SiOx /C nanorings (NRs) via AlCl3 -assisted aluminothermic reduction using dodecaphenyl cage silsesquioxane (T12 -Ph) as the building block. In this process, AlCl3 acts as both a liquid medium for reduction, and significantly as the catalyst to the cross-linking of phenyl groups in T12 -Ph. The obtained Si/SiOx /C NRs exhibits uniform diameter of ≈165 nm and well distribution of C and Si elements. The unique ring-like structure of Si/SiOx /C NRs makes it have great application potential in the field of lithium ion batteries. Notably, Si/SiOx /C NRs exhibits superior high-rate capacity and good cycle stability when used as anode for LIBs. More excitingly, Si/SiOx /C NRs can deliver a high reversible capacity of 517.9 mA h g-1 at ultra-low temperature of -70 °C, and the capacity retention as high as ≈50% of that at 25 °C. This work not only broadens structural design of carbon-based nanomaterials but also provides more possibilities for the application of POSS.

Synthesis of Tricyclic Laddersiloxane with Various Ring Sizes (Bat Siloxane).

A new synthetic method for tricyclic laddersiloxanes, ladder-type silsesquioxanes with defined structures, is developed based on intramolecular cyclization of hydrosilyl-functionalized cyclic siloxanes. This method enables the construction of unprecedented laddersiloxanes with various ring sizes. Herein, the preparation of tricyclic laddersiloxanes containing 6-8-6-, 8-8-8-, or 12-8-12-membered-ring systems is reported. These products can be considered as bat-shape siloxanes, owing to their rigid inorganic siloxane body with flexible oligosiloxane "wings" as side rings. The synthesized compounds are potential building blocks for well-defined nanomaterials, porous materials, and host molecules.

Mercapto-functionalized polyhedral oligomeric silsesquioxane as a soluble support for the synthesis of peptide thioesters.

The revival of peptide-based drugs has led to the increasing demand for the development of large-scale synthesis of these complex molecules. To meet this demand, the use of mercapto-functionalized polyhedral oligomeric silsesquioxane (POSS-SH) as a soluble support for the synthesis of a model pentapeptide POSS-thioester is reported. The synthetic process provided a total yield of 62% for the pentapeptide POSS-thioester and the 1H NMR spectra validated the high purity of the products. The successful synthesis of the pentapeptide POSS-thioester with high yield and purity provides a promising way to the scale-up chemical synthesis of peptide thioesters, peptides, peptide amides, cyclic peptides, and even proteins.

A turn-on-type fluorescence resonance energy transfer aptasensor for vibrio detection using aptamer-modified polyhedral oligomeric silsesquioxane-perovskite quantum dots/Ti3C2 MXenes composite probes.

A pair of composite probes based on aptamer modified polyhedral oligomeric silsesquioxane-perovskite quantum dots (POSS-PQDs-Apt) as signal probe and titanium carbide (Ti3C2) MXenes as quencher were prepared for the first time. They were employed to fabricate one turn-on-type aptasensor relying on fluorescence resonance energy transfer (FRET) for Vibrio parahaemolyticus (VP) determination. The POSS-PQDs-Apt can be adsorbed on the MXenes nanosheets, and its fluorescence was quenched due to the FRET. After the composite probes were incubated with VP for 50 min, the POSS-PQDs-Apt binding with VP can be released from the surface of MXenes, and the signal recovered due to its higher affinity to the VP than MXenes. The fluorescence intensity from 519 nm emission of the system was measured at 480 nm excitation. Under In optimized conditions, the assay can determine VP in the concentration range 102 - 106 cfu/mL, and the detection limit (LOD) was 30 cfu/mL using fluorescence detection. The LOD is still 100 cfu/mL by naked eye detection which is proper for on-line monitoring VP in aquaculture water. This method was also used to detect VP in actual samples of seawater, the recovery of spiked samples was between 93% and 106%, and relative standard deviation (RSD) was between 2.7% and 6.7%. The result is consistent with the plate count. Therefore, this assay could provide a candidate platform for screening VP in aquaculture industry.

Resistive Switching Characteristic Improvement in a Single-Walled Carbon Nanotube Random Network Embedded Hydrogen Silsesquioxane Thin Films for Flexible Memristors.

In this study, we evaluated the improved memristive switching characteristics of hydrogen silsesquioxane (HSQ) nanocomposites embedded with a single-walled carbon nanotube (SWCNT) random network. A low-temperature solution process was implemented using a flexible memristor device on a polyethylene naphthalate (PEN) substrate. The difference in the resistive switching (RS) behavior due to the presence of the SWCNT random network was analyzed by the current transport mechanism. Such a random network not only improves the RS operation but also facilitates a stable multilevel RS performance. The multiple-resistance states exhibited highly reliable nonvolatile retention properties over 104 s at room temperature (25 °C) and at a high temperature (85 °C), showing the possibility of an analog synaptic weight modulation. Consequently, the gradual weight potentiation/depression was realized through 3 × 102 synaptic stimulation pulses. These findings suggest that the embedded SWCNT random network can improve the synaptic weight modulation characteristics with high stability for an artificial synapse and hence can be used in future neuromorphic circuits.