Water-soluble Hybrid Research Articles

Water-Soluble Hybrid Core–Shell Nanoparticles with Titanium Dioxide Core and Poly(Acrylic Acid) Shell

Water-Soluble Hybrid Core–Shell Nanoparticles with Titanium Dioxide Core and Poly(Acrylic Acid) Shell

Enabling High-Stability of Aqueous-Processed Nickel-Rich Positive Electrodes in Lithium Metal Batteries.

Lithium batteries occupy the large-scale electric mobility market raising concerns about the environmental impact of cell production, especially regarding the use of poly(vinylidene difluoride) (teratogenic) and N-methyl-2-pyrrolidone (NMP, harmful). To avoid their use, an aqueous electrode processing route is utilized in which a water-soluble hybrid acrylic-fluoropolymer together with sodium carboxymethyl cellulose is used as binder, and a thin phosphate coating layer is in situ formed on the surface of the nickel-rich cathode during electrode processing. The resulting electrodes achieve a comparable performance to that of NMP-based electrodes in conventional organic carbonate-based electrolyte (LP30). Subsequently, an ionic liquid electrolyte (ILE) is employed to replace the organic electrolyte, building stable electrode/electrolyte interphases on the surface of the nickel-rich positive electrode (cathode) and metallic lithium negative electrode (anode). In such ILE, the aqueously processed electrodes achieve high cycling stability with a capacity retention of 91% after 1000 cycles (20 °C). In addition, a high capacity of more than 2.5 mAh cm-2 is achieved for high loading electrodes (≈15mg cm-2 ) by using a modified ILE with 5% vinylene carbonate additive. A path to achieve environmentally friendly electrode manufacturing while maintaining their outstanding performance and structural integrity is demonstrated.

Controlled Synthesis of Small Water-Soluble Hybrid Gold Nanoparticles: An Optimized Strategy for Stable Nano-Dispersion and Towards Cellular Uptake

The development of effective drug delivery systems is one of the major challenges in the fight against cancer. Gold nanoparticles could effectively harness cancer therapies by improving their potency while reducing toxic side effects. In this work, we describe a high-yield one-step synthesis of small water-soluble gold nanoparticles (AuNPs). Efficient purification was monitored, and discrete structure was fully characterized by combining molecular analytical technics (UV-visible and NMR spectroscopies) and solid-state analyses (thermal gravimetric analysis and transmission electron microscopy). These AuNPs have good dispersibility in various biocompatible media and can be used without any additives. Preliminary study with in vitro treatment of IB115 human cancer cells showed massive cellular uptake associated to moderate intrinsic cytotoxicity. The high control of the synthesis and the small size of these AuNPs are offering fine surface properties control, crucial for challenging biological nano-dispersion issues. Thus, limitation of the agglomeration of nanoparticles and improvement of interaction with the surface of cell should open new leads for vectorization of drugs or imaging probes for diagnosis.

Recent progress in the lanthanide-complexes based luminescent hybrid materials

This review mainly summarized some of the special luminescent hybrid materials using simpler and greener preparation strategy, including water-soluble hybrid materials, luminescent soft-hybrid materials based on ionic liquids, self-healing luminescent hybrid materials and luminescent hybrid materials based on bio-related materials. Particularly, this review discussed the deeper understanding of the influence on the luminescent behaviors exerted by some of inorganic matrices used to prepare the luminescent hybrid materials, and their potential applications in fields such as solar cells, LED, etc. Finally, the current challenges and future prospects in this regard be proposed. • This review mainly summarized hybrid materials using simpler and greener strategy. • This review discussed the influence on the luminescent behaviors. • The potential applications in fields of solar cells, LED were displayed. Lanthanide-based hybrid materials constructed by host–guest assembly strategy, displaying improved stability, better procesability and excellent luminescence performance simultaneously, have aroused much attention recently owing to their potential applications in various fields. This review mainly summarized some of the special luminescent hybrid materials using simpler and greener preparation strategy, including water-soluble hybrid materials, luminescent soft-hybrid materials based on ionic liquids, self-healing luminescent hybrid materials and luminescent hybrid materials based on bio-related materials. Particularly, this review discussed the deeper understanding of the influence on the luminescent behaviors exerted by some of inorganic matrices used to prepare the luminescent hybrid materials, and their potential applications in fields such as solar cells, LED, etc. Finally, the current challenges and future prospects in this regard be proposed.

Preparation of a Water-Soluble Hybrid Material with Eu(III) Complexes Modified by Graphene Oxide and Its Luminescent Film and Detection for Cu2+

A water-soluble Eu(III) hybrid composite based-on DPA and Phen as ligands, graphene oxide sheets (GOSs) as inorganic matrix, and Eu3+ as luminescence center has been synthesized, namely, Eu–DPA–Phen/GOSs. Compared with single Eu(III) complexes named Eu–DPA–Phen, Eu–DPA–Phen/GOSs not only retains the high luminescence intensity but also shows better solubility, higher stability, and longer fluorescence lifetime. It can be used as a fluorescent probe to detect Cu2+ ions in liquid medium and mixed with polyvinyl alcohol (PVA) to produce a self-supporting film with high luminescence intensity, good stability, mechanical properties. This film is also sensitive to Cu2+ ions and convenient to carry. Thus, it has a great potential in the field of flexible and foldable luminescent devices and fluorescence sensing.

New functional copolymers of 1-vinyl-1,2,4-triazole with allylamine

New water-soluble functional copolymers based on 1-vinyl-1,2,4-triazole and allylamine were synthesized under the action of free-radical initiation conditions and azobisisobutyric acid dinitrile. Сopolymers of various compositions with a molecular weight of 1287–30204 Da were obtained by varying reaction conditions. The structure, molecular weight and physicochemical properties of the copolymers were determined using elemental analysis, IR and NMR 1H-spectroscopy, gel permeation chromatography, potentiometric and turbidimetric titration, as well as dynamic light scattering and thermogravimetric analysis. It was established that the obtained copolymers, exhibiting the properties of high-resistance organic semiconductors, are characterized by a specific electrical conductivity of 10-13 – 10-14 S/cm and high resistance to thermal destruction (up to 260–280 °C). These copolymers are promising as stabilizing polymer matrices in the formation of biologically active water-soluble hybrid organic-inorganic nanocomposites.

Synthesis of selenium-containing galactomannan-stabilized nanocomposites with particle size-sensitive antiradical activity

Water-soluble hybrid nanocomposites were synthesized for the first time with the use of industrial crystalline selenium (gray powder selenium) activated in a hydrazine hydrate—alkali base-recovery system. The obtained nanocomposites consist of the selenium nanoparticles 13.0–24.0 nm in size stabilized by biocompatible natural polysaccharide galactomannan. The structures of the nanocomposites were characterized by a complex of physicochemical methods (X-ray diffraction analysis, transmission electron microscopy, and infrared spectroscopy). The pronounced antioxidant activity of the prepared nanocomposites against free radicals of 2,2-diphenyl-1-picrylhydrazyl and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt was found, and its value correlates with the particle size of selenium.

Synthesis and comparative assessment of antiradical activity, toxicity, and biodistribution of κ-carrageenan-capped selenium nanoparticles of different size: in vivo and in vitro study.

In the present study, water-soluble hybrid selenium-containing nanocomposites have been synthesised via soft oxidation of selenide-anions, preliminarily generated from elemental bulk-selenium in the base-reduction system 'N2H4-NaOH'. The nanocomposites obtained consist of Se0NPs (4.6-24.5 nm) stabilised by κ-carrageenan biocompatible polysaccharide. The structure of these composite nanomaterials has been proven using complementary physical-chemical methods: X-ray diffraction analysis, transmission electron microscopy, optical spectroscopy, and dynamic light scattering. Optical ranges of 'emission/excitation' of aqueous solutions of nanocomposites with Se0NPs of different sizes are established and the most important parameters of their luminescence are determined. For the obtained nanocomposites, the expressed antiradical activity against free radicals 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid has been found, the value of which depends on the size of selenium nanoparticles. It is experimentally revealed that all obtained nanocomposites are low toxic (LD50 >2000 mg/kg). It is also found that small selenium nanoparticles (6.8 nm), in contrast to larger nanoparticles (24.5 nm), are accumulated in organisms to significantly increase the level of selenium in the liver, kidneys, and brain (in lesser amounts) of rats.

Preparation and characterization of stable water soluble hybrid nanostructures of hydrophobic compounds by encapsulation into nanoparticles of amphiphilic N-vinylpyrrolidone copolymers of new generation

The conditions for obtaining stable aqueous solutions of prospective pharmaceutical: a lipophilic aminonitroxyl platinum complex, namely, e-amine-d-(4-amino-2, 2, 6, 6-tetramethylpiperidine 1-oxyl)-a, fbis(octanoato)-b, c-dichloroplatinum(IV) (PNC), and a dye zinc tetraphenylporphyrinate (ZnTPP) by means of their solubilization with polymer particles of N-vinylpyrrolidone with dimethacrylate. Aqueous solutions of PNC and ZnTPP encapsulated into polymer particles were investigated by dynamic light scattering, and the temperature dependence of nanostructure sizes was studied. According to transmission electron microscopy, the hybrid nanostructures are core—shell particles, in which the PtIV complex forms small clusters (∼4 nm). It was established by ESR and voltammetric measurements that the free radical fragment of the aminonitroxyl PtIV complex kept its mobility and the same ESR and redox characteristics as the 4-acetylamino-2, 2, 6, 6-tetramethylpiperidine 1-oxyl radical. The obtained results indicate that biocompatible copolymers of N-vinylpyrrolidone are of interests as carriers and delivery tools for ZnTPP and organic PtIV complexes. Hybrid structures of given dimensions and properties can be created on their basis necessary for biomedical applications.

Protein-directed crystalline 2D fullerene assemblies.

Water soluble 2D crystalline monolayers of fullerenes grow on planar assemblies of engineered consensus tetratricopeptide repeat proteins. Designed fullerene-coordinating tyrosine clamps on the protein introduce specific fullerene binding sites, which facilitate fullerene nucleation. Through reciprocal interactions between the components, the hybrid material assembles into two-dimensional 2 nm thick structures with crystalline order, that conduct photo-generated charges. Thus, the protein-fullerene hybrid material is a demonstration of the developments toward functional materials with protein-based precision control of functional elements.

Calixarene-mediated assembly of water-soluble C60-attached ultrathin graphite hybrids for efficient activation of reactive oxygen species to treat neuroblastoma cells.

Unprecedented nano-carbon hybrids consisting of exfoliated ultrathin graphite (or single-walled carbon nanotubes) with pristine C60 molecules attached on the surfaces have been produced in water in the presence of p-phosphonic acid calix[8]arene. The amphiphilic calixarene plays multiple roles in these processes to provide water dispersibility and π-π interactions with flexible conformations complementing curvatures of the carbon surfaces. The significantly increased water solubility and area of exposure of C60 enable efficient activation of reactive oxygen species for enhanced phototoxicity to SH-SY5Y human neuroblastoma cell line under laser irradiation.

Strong luminescence and sharp heavy metal ion sensitivity of water-soluble hybrid polysaccharide nanoparticles with Eu3+ and Tb3+ inclusions

In this work, we contributed new lanthanide (Eu3+ and Tb3+) complexes that were embedded in both positively and negatively charged polyelectrolyte complex nanoparticles (PCN). Luminescent Eu3+ complexes [Eu(TTA)3Phen] are formed from Eu3+ using 2-thenoyltrifluoroacetone (TTA) and 1,10-phenanothroline hydrate (Phen) as ligands. Luminescent Tb3+ complexes [Tb(AcAc)3Phen] are formed from Tb3+ using acetyl acetone (AcAc) and Phen as ligands. Then, polyelectrolyte complex nanoparticles(PCN) are applied to embed lanthanide (Eu3+ and Tb3+) complexes with two forms of positive charged and negative charged PCNs. PCN/Eu(TTA)3Phen and PCN/Tb(AcAc)3Phen show that the particle sizes are 40–60 nm and 30–80 nm, respectively. Notably, both hybrid PCN nanoparticles with Eu3+ and Tb3+ inclusions behave excellent characteristic luminescence properties. The red emission hybrid nanoparticles of PCN/Eu(TTA)3Phen indicate high luminescence intensities at low concentration of 10−5 M whereas The green emission hybrid nanoparticles of PCN/Eu(TTA)3Phen show high luminescence intensity at high concentration of 10−3 M. Furthermore, concentration-dependent luminescence quenching by heavy metal ions (Ni2+, Co2+, Cu2+, Fe3+, and Zn2+) at concentrations as low as 10−5 M is also reported. This quenching effect of heavy metal ions on the fluorescence property of PCN/Eu(TTA)3Phen and PCN/Tb(AcAc)3Phen nanoparticles will be valuable for sensing application on bio- and environmental fields. The charged polyelectrolyte polymeric shells of both PCN/Eu(TTA)3Phen and PCN/Tb(AcAc)3Phen nanoparticles make the lanthanide(Eu3+ and Tb3+) complexes be compatible in biological and aqueous environmental systems.

Covalently linked water-soluble fullerene–fluorescein dyads as highly efficient photosensitizers: Synthesis, photophysical properties and photochemical action

The synthesis, photophysical and photodynamic properties of two water-soluble hybrid structures based on the polycationic or polyanionic fullerene [60] derivative covalently linked to fluorescein are described. The significant influence of electrostatic charges on the conformation of the studied fullerene–fluorescein structures in aqueous solution and on their photophysical properties and photochemical activity was demonstrated. A polycationic fullerene derivative–fluorescein conjugate exhibits a pronounced quenching of fluorescence (more than 25 times) due to the energy and/or electron transfer from dye to fullerene. Such activation of fullerene generates reactive oxygen species greater than 15 times more effectively than an individual dye or fullerene does. In contrast, for the polyanionic fullerene derivative–fluorescein conjugate such effects are practically absent. The demonstrated effects open up wide opportunities for a directional design of highly efficient water-soluble photosensitizers by combining the singlet-excited dyes and fullerene [60] for applications in photodynamic therapy.

A Highly Selective and Sensitive Ratiometric Fluorescent Probe for Hypochlorite and Its Application

A novel water-soluble hybrid fluorescein-coumarin dye(FLNC) fluorescence ratiometric probe to recognize OCl− was designed and synthesized. The most prominent feature of the probe is that the molecular structure contains two different fluorophores, and the fluorescein moiety was connected to coumarin moiety by diacylhydrazine linker. When OCl− was added, the two fluorophores in the FLNC probe could have a rapid respond simultaneously, with high selectivity and sensitivity towards OCl– among other reactive oxygen species/reactive nitrogen species(ROS/RNS) and anions, and the detection limit was measured to be 0.30 μmol/L. In addition, the color changes of the solution could be observed by the naked eye and have a short response time(completed within 1 min), which suggestes that the probe FLNC has the potential to be used for real-time detection.

(Invited) Amphiphilic Block Copolymers and Their Hybrids for Efficient Aqueous-Processed Solar Cells

Due to their low cost and high efficiency, polymer/nanocrystal hybrid solar cells have attracted much attention in recent years. Additionally, aqueous-processed solar cells are attractive because they exhibit the potential to produce clean energy via the use of nontoxic solvents. The use of water instead of toxic organic solvents during the fabrication process of these devices is capable of significantly reducing the environmental impact as well as the production cost. In aqueous-processed solar cells, hybrid solar cells employing water-soluble conjugated polymers and inorganic nanocrystals as photovoltaic materials have gained much attention. These hybrid materials take advantage of both water-soluble conjugated polymers and nanocrystals, which exhibit adjustable absorption properties through structural modification, efficient charge carrier generation, and high charge carrier mobility. Water-soluble conjugated polymers are typically homopolymers with ionic (i.e., sulfonate and phosphonate moieties) or nonionic, hydrophilic (i.e., hydroxyl and glycol moieties) side chains. Unfortunately, the use of hydrophilic side chains in these conventional water-soluble conjugated polymers adversely affected the stacking of the polymer backbone, which can lead to the deterioration of their optoelectronic properties and thus a lower power conversion efficiency in solar cells. Furthermore, these side chains may cause charge trapping when applied in the active layer, which results in the further reduction in performance In this presentation, the use of a water-soluble hybrid material consisting of amphiphilic block copolymers and cadmium telluride nanocrystals as the active layer in hybrid solar cells will be discussed. The amphiphilic block copolymers composed of poly(3-hexylthiophene) (P3HT) and poly(acrylic acid) (PAA) self-assembled into ordered nanostructured micelles which then transformed to nanowires by co-micellization with P3HT additives. Furthermore, after annealing, the hybrid materials formed an interpenetrating network. The properties of the hybrid materials and the film morphology, and how they correlate to the device performance will be discussed.

A glycoluril dimer-triptycene hybrid receptor: synthesis and molecular recognition properties.

The strategic combination of the methylene bridged glycoluril dimer and triptycene skeletons delivers acyclic water soluble hybrid receptor 1 which is analogous to cucurbit[6]uril. The molecular recognition properties of host 1 toward hydrophobic cationic guests are investigated in detail by a combination of 1H NMR spectroscopy and isothermal titration calorimetry (ITC) studies. The fluorescence emission of 1 can be selectively and efficiently quenched upon the formation of 1·26 and 1·28 complexes.

Self-Assembled Amphiphilic Block Copolymers/CdTe Nanocrystals for Efficient Aqueous-Processed Hybrid Solar Cells.

Due to their low cost and high efficiency, polymer/nanocrystal hybrid solar cells (HSCs) have attracted much attention in recent years. In this work, water-soluble hybrid materials consisting of amphiphilic block copolymers (ABCPs) and cadmium telluride nanocrystals (CdTe NCs) were used as the active layer to fabricate the HSCs via aqueous processing. The ABCPs composed of poly(3-hexylthiophene) (P3HT) and poly(acrylic acid) (PAA) self-assembled into ordered nanostructured micelles which then transformed to nanowires by comicellization with P3HT additives. Furthermore, after annealing, the hybrid materials formed an interpenetrating network which resulted in a maximum power conversion efficiency of 4.8% in the HSCs. The properties of the hybrid materials and the film morphology were studied and correlated to the device performance. The results illustrate how the inclusion of ABCPs for directed assembly and homo-P3HT for charge transport and light absorption improves device performance. The aqueous-processed HSCs based on the ABCPs and NCs offer an effective method for the fabrication of efficient solar cells.

Unexpected "Hammerlike Liquid" to Pulverize Silica Powders to Stable Sols and Its Application in the Preparation of Sub-10 nm SiO2 Hybrid Nanoparticles with Chirality.

Silane coupling agents are well-known as surface modifiers for various kinds of silica (SiO2). However, in the present research, it has been found that they can also work as “hammerlike liquid” to pulverize different kinds of bulk amorphous SiO2 in aqueous systems. This new function was typically clarified by using 3-aminopropyltrimethoxysilane (APS) and bundles of chiral SiO2 nanofibers (with average diameter of ∼10 nm) as raw materials. By a simple reflux of the mixture of SiO2 nanofibers and excessive APS in pure H2O, the solid-containing mixture turned into a completely clear solution that contained sub-10 nm, amine-modified, and water-soluble hybrid SiO2 sols (HS-sols). Moreover, this solution showed blue luminescence under ultraviolet irradiation. Furthermore, the circular dichroism and vibrational circular dichroism spectra revealed that the HS-sols are optically active even though the pristine chiral SiO2 nanofibers were completely destroyed. It was considered that the chirality of SiO2 nanofibers was due to the asymmetric arrangement of Si and O atoms in chiral domains (<10 nm) on the Si–O–Si network of SiO2, and these domains are still preserved in chiral HS-sols. This green method has high potential for the recycling of rich SiO2 sources to obtain functional SiO2 nanomaterials with applications such as optical display, imaging, and chiral recognition. Also, it offers a tool for the analysis of the structural properties of SiO2 on the molecular scale.

Luminescence properties of hybrid associates of colloidal CdS quantum dots with J-aggregates of thiatrimethine cyanine dye

Luminescence properties of water-soluble hybrid associates of semiconductor colloidal CdS quantum dots (QDs) with average size of 2.5nm, 3.2nm, 4.2nm and J-aggregates of 3,3′-di-(γ-sulfopropyl)-4,4′,5,5′-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt (Dye) in gelatin were investigated using the methods of absorption, steady-state and time-resolved luminescence spectroscopy. The decrease in luminescence intensity of CdS QDs and increase in luminescence intensity of Dye J-aggregates were detected with increasing of Dye concentration. It was shown that curves of luminescence decay of CdS QDs are non-exponential. The decreasing of luminescence lifetime of CdS QDs with increasing of Dye J-aggregates concentration was observed. It was concluded that dynamic quenching due to non-radiative resonance energy transfer takes place. It was shown that overlap integral between luminescence spectra of CdS QDs and absorption spectra of Dye J-aggregates increases with the increase of average diameter of CdS QDs and luminescence decay of CdS QDs is accelerated. Energy transfer efficiency for all three sizes of QDs was more than 31%.

Iron-containing nanoparticles based on the 2-hydroxypropyl-β-cyclodextrin in aqueous solutions

The water-soluble hybrid nanoparticles based on high-substituted 2-hydroxypropyl-β-cyclodextrin were formed in situ during the reduction of iron(+2) salts by hypophosphite ion in alkaline medium. These nanoparticles are high sensitive to temperature and ultrasonication. It was established that the temperature and ultrasonication time of exposure increase leads to the successive dissociation of the nanoparticles.