Enantioselective Glutamic Acid Discrimination and Nanobiological Imaging by Chiral Fluorescent Silicon Nanoparticles.

Enantioselective discrimination of chiral molecules is essential in chemistry, biology, and medical science due to the configuration-dependent activities of enantiomers. Therefore, identifying a specific amino acid and distinguishing it from its enantiomer by using nanomaterials with outstanding performance are of great significance. Herein, blue- and green-emitting chiral silicon nanoparticles named bSiNPs and gSiNPs, respectively, with excellent water solubility, salt resistance, pH stability, photobleaching resistance, biocompatibility, and ability to promote soybean germination, were fabricated in a facile one-step method. Especially, chiral gSiNPs presented excellent fluorescence recognition ability for glutamic acid enantiomers within 1 min, and the enantiomeric recognition difference factor was as high as 9.0. The mechanism for enantiomeric fluorescence recognition was systematically explored by combining the fluorescence spectra with density functional theory (DFT) calculation. Presumably, the different Gibbs free energy and hydrogen-bonding interaction of the chiral recognition module with glutamic acid enantiomers mainly contributed to the difference in the fluorescence signals. Most noteworthy was the fact that the chiral gSiNPs can showcase not only the ability to recognize l- and d-glutamic acids in living cells but also the test strips fabricated by soaking gSiNPs can be applied for d-glutamic acid visual detection. As a result, this study provided insights into the design of multifunctional chiral sensing nanoplatforms for enantiomeric detection and other applications.

Controlled packing of chiral assembly scaffolds to promote chiral J-aggregation of carbocyanine dyes.

Controlled aggregation of dyes is crucial to achieve their desired optical and electronic properties. Here, we report the induction of chiral J-aggregation of carbocyanine dyes by using lysine-derived amphiphile assemblies as scaffolds in water. The molecular structure of the amphiphiles affected the packing of the assembly. The tight packing with some flexibility promoted the formation of J-aggregates of the dyes with strong chiroptical properties.

Sequential chiral induction between organic and inorganic supramolecular helical assemblies for the in situ formation of chiral carbon dots.

Self-organised helical bilayers of dicationic gemini surfactants confined in helical silica nanospace were transformed in situ to carbon dots (CDots) via pyrolysis. These water-dispersible CDots exhibit electronic absorption spanning the UV and visible range and possess symmetrical circular dichroism (CD) signals, the sign of which depends on the handedness of the helices.

Fabrication of Electrospun PLA-nHAp Nanocomposite for Sustained Drug Release in Dental and Orthopedic Applications.

This study describes the fabrication of nanocomposites using electrospinning technique from poly lactic acid (PLA) and nano-hydroxyapatite (n-HAp). The prepared electrospun PLA-nHAP nanocomposite is intended to be used for drug delivery application. A hydrogen bond in between nHAp and PLA was confirmed by Fourier transform infrared (FT-IR) spectroscopy. Degradation study of the prepared electrospun PLA-nHAp nanocomposite was conducted for 30 days both in phosphate buffer solution (PBS) of pH 7.4 and deionized water. The degradation of the nanocomposite occurred faster in PBS in comparison to water. Cytotoxicity analysis was conducted on both Vero cells and BHK-21 cells and the survival percentage of both cells was found to be more than 95%, which indicates that the prepared nanocomposite is non-toxic and biocompatible. Gentamicin was loaded in the nanocomposite via an encapsulation process and the in vitro drug delivery process was investigated in phosphate buffer solution at different pHs. An initial burst release of the drug was observed from the nanocomposite after 1 to 2 weeks for all pH media. After that, a sustained drug release behavior was observed for the nanocomposite for 8 weeks with a release of 80%, 70% and 50% at pHs 5.5, 6.0 and 7.4, respectively. It can be suggested that the electrospun PLA-nHAp nanocomposite can be used as a potential antibacterial drug carrier for sustained drug release in dental and orthopedic sector.

Chiral H-aggregation-induced large stokes shift with CPL generation assisted by α-helical poly(L-lysine) substructure.

Fluorescent materials with large Stokes shifts have significant potential for use in optical applications. Typically, a synthetic design strategy is utilized for this purpose. In this study, we demonstrated a novel method by binding a chiral template to a nonchiral fluorescent agent without chemical modification. Specifically, α-helical poly(L-lysine) was employed as the chiral template, which interacted with a disulfonic fluorescent dye, such as NK2751. The dye caused excimer luminescence by inducing the formation of a chirally H-aggregated dimer only when poly(L-lysine) was in an α-helical shape. The result was a Stokes shift of 230 nm. Similar effects were not observed when the chiral template was in a random coil condition and the Stokes shift was less than 40 nm. These findings imply that H-aggregated dimerization, which often results in quenching, permits the electronic transitions necessary for fluorescence events by the formation of the chirally twisted state. In addition, we introduce for the first time the generation of circularly polarized luminescence using the chirality induction phenomena in a dye supported by poly(L-lysine).

Zwitterionic polymer-terminated porous silica stationary phases for highly selective separation in hydrophilic interaction chromatography.

We described two novel zwitterionic polymer-terminated porous silica stationary phases containing the same pyridinium cation and anions of different side chains (carboxylate and phosphonate groups) for use in hydrophilic interaction liquid chromatography (HILIC). These two novel columns were prepared by polymerizing 4-vinylpyridine and grafting it onto a silica surface, followed by quaternization reaction with 3-bromopropionic acid (Sil-VPC24) and (3-bromopropyl) phosphonic acid (Sil-VPP24), which possess positively charged pyridinium groups, and negatively charged carboxylate and phosphonate groups, respectively. The products obtained were verified through relevant characterization techniques such as elemental analysis, Fourier-transform infrared spectroscopy, thermogravimetric analysis, Zeta potential analysis, and Brunauer-Emmett-Teller analysis. The retention properties and mechanisms of different types of compounds (neutral, cationic, and anionic) on the two zwitterionic-modified silica stationary phases were studied by varying the buffer salt concentration and pH of the eluent. The separation of phenol and aromatic acids, disubstituted benzene isomers, sulfonamide drugs, as well as nucleosides/nucleobases were investigated on the two packed novel columns and a commercial zwitterionic column in identical HILIC mode, ensuring a thorough comparison between both novel columns and with a commercial standard. The results illustrated that various compounds could be separated up to various efficiencies based on the mechanism of hydrophilic interaction-based retention between the solutes and the two zwitterionic polymer stationary phases. The Sil-VPP24 column demonstrated the best separation performance out of the three, as well as flexible selectivity and excellent resolution. Both novel columns exhibited excellent stability and chromatographic repeatability for the separation of seven nucleosides and bases.

Carbonized π-conjugated polymer-coated porous silica: preparation and evaluating its extraction ability for berberine.

In view of the limitations of existing berberine solid-phase extraction adsorbents, this paper proposes a novel carbonized π-conjugated polymer-coated porous silica (SiO2@C-π-CP) adsorbent with simple process and low cost for efficient extraction of berberine by multiple interactions. Characterization methods, including Brunner-Emmet-Teller measurement, thermogravimetric analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy techniques, were used to verify the successful modification of carbonized π-conjugated polymer on the surface of porous silica. The berberine was selected as target molecule, and the adsorption mechanism and process were investigated through adsorption kinetics, adsorption isotherms, and thermodynamic studies. The fitting results show that the adsorption of berberine by SiO2@C-π-CP well conforms to the pseudo-second-order and Langmuir models. By optimizing the main SPE parameters, the SPE method based on SiO2@C-π-CP was developed. Excellent results were obtained, including low limit of detection (0.75 ng mL-1) and limit of quantification (2 ng mL-1), wide linearity (2-13,000 ng mL-1), and satisfactory relative standard deviations (RSD) of inter-day (1.5%) and intra-day (6.2%). Finally, the SiO2@C-π-CP also has been successfully used to the enrichment of berberine in real urine samples. This research makes clear that SiO2@C-π-CP has outstanding potential for trace enrichment of berberine alkaloids.

Advanced CNC/PEG/PDMAA Semi-IPN Hydrogel for Drug Delivery Management in Wound Healing.

A Semi Interpenetrating Polymer Network (semi-IPN) hydrogel was prepared and loaded with an antibiotic drug, gentamicin, to investigate the wound healing activity of this system. The semi-IPN hydrogel was synthesized by combining natural polymer cellulose nanocrystal (CNC) and synthetic polymer polyethylene glycol (PEG) and poly (N,N'-dimethyl acrylamide) (PDMAA), which was initially added as a monomer dimethyl acrylamide (DMAA). CNC was prepared from locally obtained jute fibers, dispersed in a PEG-NaOH solvent system and then mixed with monomer DMAA, where polymerization was initiated by an initiator potassium persulphate (KPS) and cross-linked by N,N'-methylenebisacrylamide (NMBA). The size, morphology, biocompatibility, antimicrobial activity, thermal and swelling properties of the hydrogel were investigated by different characterization techniques. The biocompatibility of the hydrogel was confirmed by cytotoxicity analysis, which showed >95% survival of the BHK-21, Vero cell line. The drug loaded hydrogel showed antimicrobial property by forming 25 and 23 mm zone of inhibition against Staphylococcus aureus (gram-positive) and Escherichia coli (gram-negative) bacteria, respectively, in antimicrobial analysis. At pH 5.5, 76% of the drug was released from the hydrogel within 72 h, as observed in an in vitro drug release profile. In an in vivo test, the healing efficiency of the drug loaded hydrogel was examined on a mice model with dorsal wounds. Complete healing of the wound without any scar formation was achieved in 12 days, which revealed excellent wound healing properties of the prepared drug loaded semi-IPN hydrogel. These results showed the relevance of such a system in the rapid healing of acute wounds.

Chemical redox-induced chiroptical switching of supramolecular assemblies of viologens.

A chiral supramolecular assembly exhibiting redox-induced changes in its chiroptical properties was prepared using viologen-modified glutamide (G-V2+) derivatives. Achiral viologen moieties in the G-V2+ assembly were chirally orientated by glutamide groups, affording a unique orange-colored solution, with a visible absorption band at around 470 nm, having electronic circular dichroism (CD) signals (molar ellipticity [θ] = 0.58 × 105 deg cm2 dmol-1: absorption dissymmetry factors (g) = 5.2 × 10-3 at 512 nm). The G-V2+ could be reduced to its cation radical (G-V+˙) but retains its chiral assembly. After chemical reduction, the color change from orange to blueish violet, indicating an absorption band at approximately 560 nm, and the sign change of the CD signal from positive to negative ([θ] = -0.36 × 105 deg cm2 dmol-1; g = -2.9 × 10-3 at 580 nm) were observed in water. Subsequent oxidation re-introduces the G-V2+ chiroptical behavior before reduction.

A Molecular Shape Recognitive HPLC Stationary Phase Based on a Highly Ordered Amphiphilic Glutamide Molecular Gel.

Chiral glutamide-derived lipids form self-assembled fibrous molecular gels that can be used as HPLC organic phases. In this study, HPLC separation efficiency was improved through the addition of branched amphiphilic glutamide lipids to the side chains of a terminally immobilized flexible polymer backbone. Poly(4-vinylpyridine) with a trimethoxysilyl group at one end was grafted onto the surface of porous silica particles (Sil-VP15, polymerization degree = 15), and the pyridyl side chains were quaternized with a glutamide lipid having a bromide group (BrG). Elemental analysis indicated that the total amount of the organic phase of the prepared stationary phase (Sil-VPG15) was 38.0 wt%, and the quaternization degree of the pyridyl groups was determined to be 32.5%. Differential scanning calorimetric analysis of a methanol suspension of Sil-VPG15 indicated that the G moieties formed a highly ordered structure below the phase transition temperature even on the silica surface, and the ordered G moieties exhibited a gel-to-liquid crystalline phase transition. Compared with a commercially available octadecylated silica column, the Sil-VPG15 stationary phase showed high selectivity toward polycyclic aromatic hydrocarbons, and particularly excellent separations were obtained for geometrical and positional isomers. Sil-VPG15 also showed highly selective separation for phenol derivatives, and bio-related molecules containing phenolic groups such as steroids were successfully separated. These separation abilities are probably due to multiple interactions between the elutes and the highly ordered functional groups, such as the pyridinium and amide groups, on the highly ordered molecular gel having self-assembling G moieties.

Enantioselective Self-Assembled Nanofibrillar Network with Glutamide-Based Organogelator.

A chiral molecular gelation system, as a chiral host, was used to effectively realize enantioselectivity using the simple carboxylic acid functional group. For this purpose, an L-glutamic-acid-based lipidic amphiphile (G-CA) with a carboxylic head group was selected and its responsiveness to cationic guest molecules was investigated. The dispersion morphology of G-CA in its solution state was examined by confocal and transmission electron microscopies, while interactions between the G-CA, as the host system, and guest molecules were evaluated by UV-visible, circular dichroism, and fluorescence spectroscopies. As a result, enantioselectivity was effectively induced when G-CA formed highly ordered aggregates that provide negatively charged surfaces in which carboxyl groups are assembled in highly ordered states, and when the two cationic groups of the guest molecule are attached to this surface through multiple interactions.

Lanthanide ion-doped silica nanohelix: a helical inorganic network acts as a chiral source for metal ions.

We demonstrate that lanthanide ions doped in nanometrical silica helices with a chirally arranged siloxane network without any organic mediates show induced chiroptical properties such as circular dichroism and circularly polarized luminescence.

Hetero-network hydrogels crosslinked with silica nanoparticles for strategic control of thermal responsive property.

Two thermoresponsive copolymers with different lower critical solution temperatures (LCSTs) were crosslinked using silica nanoparticles to afford hybrid hydrogels exhibiting two distinct thermo-responsivities. The thermo-responsive copolymers were synthesised by free radical polymerisation from a monomer with a reactive side chain (3-methacryloxypropyl trimethoxysilane (S)) and water-soluble monomers with different thermo-responsivities (N-isopropyl acrylamide (N) or N-(3-methoxy propyl)acrylamide (M)). The obtained reactive copolymers, poly(N-isopropyl acrylamide-co-3-methacryloxypropyl trimethoxysilane) (pNS) and poly(N-(3-methoxy propyl acrylamide-co-3-methacryloxypropyl trimethoxysilane)) (pMS), were characterized by multiple techniques including 1H NMR and FTIR spectroscopy. The hetero-network hybrid hydrogels were easily prepared by mixing aqueous solutions of the copolymer with an aqueous colloidal silica suspension; their gelation properties could be tuned by varying the amounts of pNS, pMS, and Si. Differential scanning calorimetric analysis showed that the hetero-network hydrogel exhibited a critical two-step phase transition at temperatures around the LCST of each copolymer (33 °C for pNS, 73 °C for pMS), indicating that each polymer does not disturb the phase transitions of the other. The deswelling of the hetero-network hydrogel could be controlled with respect to temperature and time.

Remarkable enhancement of thermal stability of epoxy resin through the incorporation of mesoporous silica micro-filler.

For the first time, we incorporated mesoporous micro-silica (5 µm, pore size = 50 nm) as a filler in epoxy resin aiming to enter polymer into the pore of the silica. As expected, the thermal stability of the composite increased remarkably, followed by noteworthy thermal degradation kinetics when compared to the controlled cured epoxy resin. Composites were prepared by the direct dispersion of modified nano-silica, modified mesoporous micro-silica, unmodified mesoporous micro-silica, non-porous micro-silica, and irregular micro-silica of various pore sizes as fillers in diglycidyl ether of bisphenol-A epoxy resin via ultra-sonication and shear mixing, followed by oven-curing with 4,4-diaminodiphenyl sulfone. DSC and TGA analyses demonstrated a higher glass transition temperature (increased by 3.65-5.75 °C) and very high activation energy for thermal degradation (average increase = 46.2%) was obtained for the same unmodified silica composite compared to pure epoxy, respectively.

Fabrication of Carbon-Like, π-Conjugated Organic Layer on a Nano-Porous Silica Surface.

This paper presents a new type of black organic material-porous silica composite providing an extremely highly selective adsorption surface. This black composite was prepared by lamination on nano-sized pores with a carbon-like, π-extended structure, which can be converted via the on-site polymerization of 1,5-dihydroxynaphthalene with a triazinane derivative and a thermally induced condensation reaction with denitrification. This bottom-up fabrication method on porous materials had the great advantage of maintaining the pore characteristics of a raw porous material, but also the resultant black surface exhibited an extremely high molecular-shape selectivity; for example, that for trans- and cis-stilbenes reached 14.0 with the black layer-laminated porous silica, whereas it was below 1.2 with simple hydrophobized silica.

Chirality induction on non-chiral dye-linked polysilsesquioxane in nanohelical structures.

We demonstrate the direct induction of chirally arranged organic dye-linked polysilsesquioxane through a sol-gel transcription using a chiral supramolecular template. The chiral arrangement was confirmed by using electronic and vibrational circular dichroism and circularly polarized luminescence spectroscopies.

Extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in glutamide-based molecular gels.

Aggregation-induced chirality is potentially useful in sensor technology applications. Herein we show extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in molecular gels. The secondary chirality reflecting on enhancement of chiral signals (i.e., circular dichroism (CD) and circularly polarised luminescence (CPL)) of the molecular gels formed from glutamide-attached terpyridine (G-tpy) is extremely enhanced by the coordination of its terpyridyl groups to metal ions such as Cu2+, Zn2+ and Ru2+, which is due to dramatic changes in the stacked structure of the chromophore groups through the formation of metal ion complex. Metal-free terpyridine exists in a non-planar geometry, which suppress π-π stacking interactions among aggregates. The planarity of the terpyridyl group is improved through metal-ion complexation, which induces the metal-ion-coordinated terpyridyl groups to stack. The thermal stabilities of the CD signals are strongly affected by the metal-ion species. CPL signal is generated in the molecular gel formed from G-tpy-Zn2+ complex accompanied by chelation-enhanced fluorescence. It is expected that large and sensitive coordination-driven secondary chirality signals (CD and CPL) are useful for sensing guest molecules and the surrounding environment.

Emission-Color Control in Polymer Films by Memorized Fluorescence Solvatochromism in a New Class of Totally Organic Fluorescent Nanogel Particles.

In this work, a new class of totally organic fluorescent nanogel particles and their exceptionally specific behaviors based on their unique structures are introduced, which draws a sharp line from conventional fluorophore-doped and fluorophore-branched-type particles. The nanogel particles, the diameter of which could be controlled by adjusting reaction conditions, such as the solvent system, were spontaneously fabricated with a spherical shape by direct polymerization of non-heterocyclic aromatic compounds, such as 2,6-dihydroxyanthracene, 2,6-dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene with triazinane as the cross-linker. A fluorophoric moiety formed from a polymer main chain was realized in the particle, and consequently, the resultant content of the fluorophoric moiety was around 70-80 wt % per particle. The uniqueness and versatility of the particles can be emphasized by their good compatibility with various solvents due to their amphiphilic and ampholytic swelling properties, but also by their remarkable fluorescent solvatochromism in the dispersion state. Furthermore, these behaviors were preserved even in their polymer composite system. This study also demonstrates that various fluorescent polymer films can be fabricated with emission color control due to memorization of the solvatochromism phenomenon of the dispersed fluorescent nanoparticles.

Preparation of High Refractive Index Composite Films Based on Titanium Oxide Nanoparticles Hybridized Hydrophilic Polymers.

Optical materials with high refractive index (n) have been rapidly improved because of urgent demands imposed by the development of advanced photonic and electronic devices such as solar cells, light emitting diodes (LED and Organic LED), optical lenses and filters, anti-reflection films, and optical adhesives. One successful method to obtain high refractive index materials is the blending of metal oxide nanoparticles such as TiO2 and ZrO2 with high n values of 2.1-2.7 into conventional polymers. However, these nanoparticles have a tendency to agglomerate by themselves in a conventional polymer matrix, due to the strong attractive forces between them. Therefore, there is a limitation in the blending amount of inorganic nanoparticles. In this paper, various hydrophilic polymers such as poly(N-hydroxyl acrylamide) (pHEAAm), poly(vinyl alcohol), poly(ethylene glycol), and poly(acrylic acid) were examined for preparation of high refractive index film based on titanium oxide nanoparticle (TiNP) dispersed polymer composite. The hydrogen bonding sites in these hydrophilic polymers would improve the dispersibility of inorganic nanoparticles in the polymer matrix. As a result, pHEAAm exhibited higher compatibility with titanium oxide nanoparticles (TiNPs) than other water-soluble polymers. Transparent hybrid films were prepared by mixing pHEAAm with TiNPs and drop casting the mixture onto a glass plate. The refractive indices of the films were in good agreement with calculated values. The compatibility of TiNPs with pHEAAm was dependent on the surface characteristics of TiNPs. TiNPs with the highest observed compatibility could be hybridized with pHEAAm at concentrations of up to 90 wt%, and the refractive index of the corresponding film reached 1.90. The high compatibility of TiNPs with pHEAAm may be related to the hydrophilicity and amide and hydroxyl moieties of pHEAAm, which cause hydrogen bond formation on the TiO2 surface. The obtained thin film was slightly yellow due to the color of the original TiNP dispersion; however, the transmittance of the film was higher than 80% in the wavelength range from 480 to 900 nm.

Preparation and characterization of a novel hydrophilic interaction/ion exchange mixed-mode chromatographic stationary phase with pyridinium-based zwitterionic polymer-grafted porous silica.

Novel zwitterionic polymer-grafted porous silica microspheres were prepared by using sodium 2-bromoethanesulfonate to quaternize the pyridyl side chains of the polymer, which is anchored on the surface of porous silica. The separation behavior for toluene and benzoic acid proved that the zwitterionic polymer-grafted porous silica worked as a stationary phase in hydrophilic interaction/ion exchange mixed-mode chromatography. Compared with a conventional sulfobetaine-based zwitterion-grafted porous silica column, the prepared poly(vinylpyridinium ethanesulfonate)-immobilized porous silica afforded the highly selective separation of benzoic acid derivatives over a wide pH range, and the separation behavior was quite sensitive to the protonation state of the carboxylic acids. The high selectivity was attributed to the multiple interactions between the guest molecule and the zwitterionic groups on the polymer chains. The new zwitterionic stationary phase demonstrated excellent selectivity for hydrophilic biorelated molecules such as nucleobases and nucleosides.