Chiral Nanostructures from Helical Copolymer–Metal Complexes: Tunable Cation–π Interactions and Sergeants and Soldiers Effect

Poly(phenylacetylene) (PPA) copolymers containing (R)‐ or (S)‐MPA as minor chiral pendant can be forced to selectively adopt the right‐ o left‐handed helix, in the presence of small amounts of Na⁺ or Ag⁺ (“Sergeants and Soldiers Effect”) by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation–π interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent.     

Electrospun Nanoparticle–Nanofiber Composites via a One‐Step Synthesis

A facile approach to synthesize and incorporate metal nanoparticles (NPs) into electrospun polymer nanofibers (NFs) wherein the electrospinning polymer acts as both a reducing agent for the metal salt precursor, as well as a protecting and templating agent for the ensuing NPs, is reported. Such a true one‐step process at ambient conditions and free of organic solvents is demonstrated using a system comprising AgNO₃ and poly(ethylene oxide) (PEO) at electrospinnable molecular weights of 600, 1000, or 2000 kDa. The PEO transforms Ag⁺ into AgNPs, a phenomenon that has not been previously possible at PEO molecular weights less than 20 kDa without the addition of a separate reducing agent and stabilizer or the application of heat. Results from X‐ray photoelectron spectroscopy and UV–Vis absorption spectrophotometry analyses support the formation of pseudo‐crown ethers in high molecular weight PEO as the mechanism in the development of NPs. The AgNPs reduce fiber diameter and enhance fiber quality (reduced beading) due to increased electrical conductivity. Interestingly, several of the NFs exhibit AgNP‐localized nanochain formation and protrusion from the NF surface that can be attributed to the combined effect of applied electrical field on the polymer and the differences between the electrical conductivity and polarizability of the polymer and metal NPs.     

Double‐Layer Polymer Electrolyte for High‐Voltage All‐Solid‐State Rechargeable Batteries

No single polymer or liquid electrolyte has a large enough energy gap between the empty and occupied electronic states for both dendrite‐free plating of a lithium‐metal anode and a Li⁺ extraction from an oxide host cathode without electrolyte oxidation in a high‐voltage cell during the charge process. Therefore, a double‐layer polymer electrolyte is investigated, in which one polymer provides dendrite‐free plating of a Li‐metal anode and the other allows a Li⁺ extraction from an oxide host cathode without oxidation of the electrolyte in a 4 V cell over a stable charge/discharge cycling at 65 °C; a poly(ethylene oxide) polymer contacts the lithium‐metal anode and a poly(N‐methyl‐malonic amide) contacts the cathode. All interfaces of the flexible, plastic electrolyte remain stable with no visible reduction of the Li⁺ conductivity on crossing the polymer/polymer interface.     

Ag+‐Gated Surface Chemistry of Gold Nanoparticles and Colorimetric Detection of Acetylcholinesterase

Chemical regulation of enzyme‐mimic activity of nanomaterials is challenging because it requires a precise understanding of the surface chemistry and mechanism, and rationally designed applications. Herein, Ag⁺‐gated peroxidase activity is demonstrated by successfully modulating surface chemistry of cetyltrimethylammonium bromide‐capped gold nanoparticles (CTAB‐AuNPs). A surface blocking effect of long‐chain molecules on surfaces of AuNPs that inhibit peroxidase activity of AuNPs is found. Ag⁺ ions can selectively bind on the surfaces of AuNPs and competitively destroy CTAB membrane forming Ag⁺@CTAB‐AuNPs complexes to result in enhanced peroxidase activity. Ag⁺@CTAB‐AuNPs show the highest peroxidase activity compared to similar‐sized citrate‐capped and ascorbic acid‐capped AuNPs. Ag⁺@CTAB‐AuNPs can potentially develop into analyte‐responsive systems and exhibit advantages in the optical sensing field. For example, the Ag⁺@CTAB‐AuNPs system shows an enhanced sensitivity and selectivity for acetylcholinesterase activity sensing compared to other methods.     

Cover Picture: UV‐Light‐Induced Swelling and Visible‐Light‐Induced Shrinking of a TiO2‐Containing Redox Gel (Adv. Mater. 9/2007)

Polyacrylate gels containing Ag⁺ and TiO₂ nanoparticles are shown to swell under UV light and shrink under visible light in water. In work reported by Tetsu Tatsuma and co‐workers on p. 1249, the TiO₂ absorbs UV light and reduces the Ag⁺, whereas the deposited Ag absorbs visible light and dissolves itself. These redox reactions change the interactions between the polymer chains and eventually the volume of the gel, as shown on the cover.     

PLGA/Ag nanocomposites: in vitro degradation study and silver ion release

New nanocomposite films based on a biodegradable poly (DL-Lactide-co-Glycolide) copolymer (PLGA) and different concentration of silver nanoparticles (Ag) were developed by solvent casting. In vitro degradation studies of PLGA/Ag nanocomposites were conducted under physiological conditions, over a 5 week period, and compared to the behaviour of the neat polymer. Furthermore the silver ions (Ag⁺) release upon degradation was monitored to obtain information on the properties of the nanocomposites during the incubation. The obtained results suggest that the PLGA film morphology can be modified introducing a small percentage of silver nanoparticles that do not affect the degradation mechanism of PLGA polymer in the nanocomposite. However results clearly evinced the stabilizing effect of the Ag nanoparticles in the PLGA polymer and the mineralization process induced by the combined effect of silver and nanocomposite surface topography. The Ag⁺ release can be controlled by the polymer degradation processes, evidencing a prolonged antibacterial effect.     

Highly Selective Dispersion of Carbon Nanotubes by Using Poly(phenyleneethynylene)‐Guided Supermolecular Assembly

Isolation of single‐walled carbon nanotubes (SWNTs) with specific chirality and diameters is critical for achieving optimum performance of SWNTs in various applications. A water‐soluble π‐conjugated polymer, poly[(m‐phenyleneethynylene)‐alt‐(p‐phenyleneethynylene)], 3 , is found to exhibit high selectivity in dispersing SWNT (6,5). The polymer's ability to sort out SWNT (6,5) appears to be related to the carbon–carbon triple bond, whose free rotation allows a unique assembly of chromophores in a helical conformation. The observation is consistently supported by fluorescence, Raman, and UV‐vis‐NIR absorption spectra. The intriguing selectivity of 3 to SWNT (6,5), however, is not observed for the vinylene analogue polymer 1 , showing that the carbon–carbon triple bond could play a unique role in sorting out a specific SWNT. The observed selectivity from 3 could be attributed to a combination of the helical cavity size restrain and electronic interaction associated with the local chromophore arrangement. This strategy could be expanded for efficient SWNT sorting when the helical conformation is further finely tuned.     

Albumin Microspheres: effect of process Variables on size Distribution and in Vitro Release

Abstract

Albumin microspheres used as target drug delivery systems were prepared from egg albumin by polymerization technique using glutaral dehyde as the cross linking agent. The present study was designed to evaluate the effect of process variables on the nicrosphere size distribution and in vitro drug release. Phase volume ratio and speed of agitation exerted greater influence on the microsphere size distribution whereas the albumin concentration and cross linking time effected only the yield and surface characteristics of the microspheres respectively. Lower phase volume ratios resulted in small and uniform microspheres with smooth surfaces in narrow size range. Speed of agitation exhibited an inverse relationship with size. In vitro release pattern of drug from the microspheres showed a biphasic profile and the release rates were prolonged upon increase in the concentration of cross linking agent and cross linking time.     

Antibacterial and biological properties of silver-loaded coralline hydroxyapatite

The antibacterial and biological properties of silver-loated coralline hydroxyapatite (Ag-CHA) as a new antibacterial implant material were investigated in this study. Compared to other antibiotic and chemical bactericidal agents, Ag⁺ does not bring bacterial resistance to drugs and has less toxicity. The porous CHA was formed by hydrothermal exchange, then Ag⁺ was loated onto CHA through ion exchange and adsorption. The microstructure and composition of Ag-CHA were characterized by scanning electron microscopy (SEM), Rutherford backscattering spectrometry (RBS), and energy dispersive spectrometry (EDS). Antibacterial activity of Ag-CHA on the clinical strains of Escherichia coli (E. Coli) and Staphylococcus aureus (S. Aureus) was evaluated by the flat plate diffusion method. The antibacterial activity of Ag-CHA was found to be correlated with the concentration of Ag⁺ in a dose-dependent manner, which indicated that the optimal antibacterial and biocompatible effects of Ag-CHA could be obtained with Ag⁺ concentrations from 5×10⁻⁵ to 1×10⁻⁴ mol/L.     

Chitosan based mucoadhesive nanoparticles of ketoconazole for bioavailability enhancement: formulation,optimization, in vitro and ex vivo evaluation

Purpose: The conventional dosage form of Ketoconazole (KZ) shows poor absorption due to rapid gastric emptying. Chitosan based mucoadhesive nanoparticles (NPs) of KZ were developed to efficiently release drug at its absorption window i.e. stomach and the site of action i.e. esophagus.

Method: The NPs were prepared by ionic gelation method. Concentration of polymer, cross-linking agent and ratio of drug/polymer as well as polymer/cross linking agent were optimized.

Results: NPs had 69.16?±?5.91% mucin binding efficiency, particle size of 382.6?±?2.384?nm, ζ potential of +48.1?mv and entrapment efficiency of 59.84 ± 1.088%. DSC thermogram indicated absence of any drug polymer interaction. The drug release was by controlled, non-fickian diffusion mechanism. Ex vivo diffusion studies were performed by emptying the stomach contents after 2?h to simulate in vivo gastric emptying. The results showed that drug diffusion from the solution across stomach mucosa stopped after emptying whereas that from the NPs continued upto 5?h. Hence we could conclude that the NPs must have adhered to the stomach mucosa and thereby would have been retained at this absorption site even after gastric emptying.

Conclusion: The orally delivered KZ loaded mucoadhesive NPs can be used as an efficient carrier for delivering drug at its absorption window i.e. the stomach and the site of action i.e. esophagus even after gastric emptying.     

Luteinizing hormone‐releasing hormone targeted poly(methyl vinyl ether maleic acid) nanoparticles for doxorubicin delivery to MCF‐7 breast cancer cells

The purpose of this study was to design a targeted anti‐cancer drug delivery system for breast cancer. Therefore, doxorubicin (DOX) loaded poly(methyl vinyl ether maleic acid) nanoparticles (NPs) were prepared by ionic cross‐linking method using Zn²⁺ ions. To optimise the effect of DOX/polymer ratio, Zn/polymer ratio, and stirrer rate a full factorial design was used and their effects on particle size, zeta potential, loading efficiency (LE, %), and release efficiency in 72 h (RE₇₂, %) were studied. Targeted NPs were prepared by chemical coating of tiptorelin/polyallylamin conjugate on the surface of NPs by using 1‐ethyl‐3‐(3‐dimethylaminopropyl) carboiimid HCl as cross‐linking agent. Conjugation efficiency was measured by Bradford assay. Conjugated triptorelin and targeted NPs were studied by Fourier‐transform infrared spectroscopy (FTIR). The cytotoxicity of DOX loaded in targeted NPs and non‐targeted ones were studied on MCF‐7 cells which overexpress luteinizing hormone‐releasing hormone (LHRH) receptors and SKOV3 cells as negative LHRH receptors using Thiazolyl blue tetrazolium bromide assay. The best results obtained from NPs prepared by DOX/polymer ratio of 5%, Zn/polymer ratio of 50%, and stirrer rate of 960 rpm. FTIR spectrum confirmed successful conjugation of triptorelin to NPs. The conjugation efficiency was about 70%. The targeted NPs showed significantly less IC₅₀ for MCF‐7 cells compared to free DOX and non‐targeted NPs.Inspec keywords: nanoparticles, polymer blends, cancer, cellular biophysics, drug delivery systems, drugs, biomedical materials, zinc, positive ions, Fourier transform infrared spectra, nanomedicine, proteinsOther keywords: luteinizing hormone‐releasing hormone, poly(methyl vinyl ether maleic acid), doxorubicin delivery, MCF‐7 breast cancer cell, anticancer drug delivery system, doxorubicin‐loaded PVM‐MA nanoparticle, ionic cross‐linking method, zinc ion, doxorubicin‐polymer ratio effect, zinc‐polymer ratio effect, particle size, zeta potential, loading efficiency, release efficiency, chemical coating, tiptorelin‐polyallylamin conjugation, PVM‐MA nanoparticle surface, 1‐ethyl‐3‐(3‐dimethylaminopropyl) carboiimid HCl, cross‐linking agent, Bradford assay, Fourier transform infrared spectroscopy, cytotoxicity, LHRH receptor, SKOV3 cell, Thiazolyl blue tetrazolium bromide assay, conjugation efficiency, time 72 h, Zn²⁺      

Palm‐Sized Ag+ Ion Emission Gun Operated at Room Temperature in Non‐Vacuum Atmosphere

Ion implantation is an effective method for changing surface properties and inducing various functionalities. However, a high vacuum is generally necessary for ion implantation, which limits the range of applications. Here, we describe a palm‐sized Ag⁺ ion emission gun produced using a solid electrolyte. AgI–Ag₂O–B₂O₃ glass, known as a super‐ion‐conducting glass, has a Ag⁺ ion conductivity higher than 5 × 10^?3 S cm^?1 at room temperature. In addition, the melted glass has suitable viscous flow, and a sharp glass‐fiber emitter with a pyramid‐like apex can be obtained. Ag⁺ ion emission is observed from the tip of the glass fiber at accelerating voltages corresponding to electric fields above 20 kV cm^?1, even at room temperature in a non‐vacuum atmosphere. Ag nanoparticles of size 50–350 nm are precipitated on a Si target substrate. Other glass components such as boron and iodine are not detected. Electrochemical quartz crystal microbalance (EQCM) measurements show that the mass of Ag nanoparticles estimated from the emission current using Faraday's law of electrolysis is in good agreement with that estimated from the QCM frequency shift.

     

Ultrasmall Pb:Ag2S Quantum Dots with Uniform Particle Size and Bright Tunable Fluorescence in the NIR‐II Window

Ag₂S quantum dots (QDs) are well‐known near‐infrared fluorophores and have attracted great interest in biomedical labeling and imaging in the past years. However, their photoluminescence efficiency is hard to compete with Cd‐, Pb‐based QDs. The high Ag⁺ mobility in Ag₂S crystal, which causes plenty of cation deficiency and crystal defects, may be responsible mainly for the low photoluminescence quantum yield (PLQY) of Ag₂S QDs. Herein, a cation‐doping strategy is presented via introducing a certain dosage of transition metal Pb²⁺ ions into Ag₂S nanocrystals to mitigate this intrinsic shortcoming. The Pb‐doped Ag₂S QDs (designated as Pb:Ag₂S QDs) present a renovated crystal structure and significantly enhanced optical performance. Moreover, by simply adjusting the levels of Pb doping in the doped nanocrystals, Pb:Ag₂S QDs with bright emission (PLQY up to 30.2%) from 975 to 1242 nm can be prepared without altering the ultrasmall particle size (≈2.7–2.8 nm). Evidently, this cation‐doping strategy facilitates both the renovation of crystal structure of Ag₂S QDs and modulation of their optical properties.     

Tunable Color Temperatures and Efficient White Emission from Cs2Ag1−xNaxIn1−yBiyCl6 Double Perovskite Nanocrystals

Recently, Bi‐doped Cs₂Ag_0.6Na_0.4InCl₆ lead‐free double perovskites demonstrating efficient warm‐white emission have been reported. To enable the solution processing and enrich the application fields of this promising material, here a colloidal synthesis of Cs₂Ag_1?xNa_xIn_1?yBi_yCl₆ nanocrystals is further developed. Different from its bulk states, the emission color temperatures of the nanocrystal can be tuned from 9759.7 to 4429.2 K by Na⁺ and Bi³⁺ incorporation. Furthermore, the newly developed nanocrystals can break the wavefunction symmetry of the self‐trapped excitons by partial replacement of Ag⁺ ions with Na⁺ ions and consequently allow radiative recombination. Assisted with Bi³⁺ ions doping and ligand passivation, the photoluminescence quantum yield of the Cs₂Ag_0.17Na_0.83In_0.88Bi_0.12Cl₆ nanocrystals is further promoted to 64%, which is the highest value for lead‐free perovskite nanocrystals at present. The new colloidal nanocrystals with tunable color temperature and efficient photoluminescence are expected to greatly advance the research progress of lead‐free perovskites in single‐emitter‐based white emitting materials and devices.     

Synthesis and properties of a zinc cadmium sulfide based low-voltage cathodoluminescent phosphors

This paper describes the fabrication of a red-orange-emitting (Zn,Cd)S:(Ag,In,Sb) cathodoluminescent phosphor which offers enhanced brightness at a low excitation voltage. The effects of antimony and chlorine added to the starting mixture as coactivators are analyzed. The largest brightness gain, observed at C _Sb/C _Ag ≃ 1.3, is probably due to the formation of Ag⁺-Sb³⁺ associates. Increasing the C _Sb/C _Ag ratio to above ≃ 2.2 leads to quenching of luminescence.     

Stimuli‐Directed Colorimetric Interconversion of Helical Polymers Accompanied by a Tunable Self‐Assembly Process

Interconversion between extended and bent structures at the pendant groups of a chiral polyene framework [poly(phenylacetylene) with (R)‐(2‐methoxy‐2‐phenylacetyl)glycine residues linked to 4‐vinylanilines] allows the reversible colorimetric transformation from stretched to compressed helical cis‐transoid polyenic structures through manipulation of the flexible spacer. This transformation generates either organogels (stretched helical form) or nanoparticles (compressed helical form) under the control of polar/low polar stimuli respectively and opens the way to the development of new sensors and stimuli‐sensitive materials based on these concepts.     

Toxicity of Silver Nanoparticles in Macrophages

Silver nanoparticles (nanosilver) are broadly used today in textiles, food packaging, household devices and bioapplications, prompting a better understanding of their toxicity and biological interactions. In particular, the cytotoxicity of nanosilver with respect to mammalian cells remains unclear, because such investigations can be biased by the nanosilver coatings and the lack of particle size control. Here, nanosilver of well‐defined size (5.7 to 20.4 nm) supported on inert nanostructured silica is produced using flame aerosol technology. The cytotoxicity of the prepared nanosilver with respect to murine macrophages is assessed in vitro because these cells are among the first to confront nanosilver upon its intake by mammals. The silica support facilitates the dispersion and stabilization of the prepared nanosilver in biological suspensions, and no other coating or functionalization is applied that could interfere with the biointeractions of nanosilver. Detailed characterization of the particles by X‐ray diffraction and electron microscopy reveals that the size of the nanosilver is well controlled. Smaller nanosilver particles release or leach larger fractions of their mass as Ag⁺ ions upon dispersion in water. This strongly influences the cytotoxicity of the nanosilver when incubated with murine macrophages. The size of the nanosilver dictates its mode of cytotoxicity (Ag⁺ ion‐specific and/or particle‐specific). The toxicity of small nanosilver (<10 nm) is mostly mediated by the released Ag⁺ ions. The influence of such ions on the toxicity of nanosilver decreases with increasing nanosilver size (>10 nm). Direct silver nanoparticle–macrophage interactions dominate the nanosilver toxicity at sizes larger than 10 nm.     

Synthesis of worm-like Ag2S nanocrystals in W/O reverse microemulsion

High-aspect-ratio of worm-like Ag₂S nanocrystal with length up to several micrometers and a diameter of 25-50 nm has been successfully prepared by a Triton X-100/cyclohexane/hexanol/water W/O reverse microemulsion in the presence of TAA (Thioacetamide) as a sulfur source and EDTA (ethylene diamine tetraacetic acid) as a chelating ligand. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance absorption spectra. The results indicate that the morphology and size of Ag₂S nanocrystal can be readily controlled by modulating the mole ratio of Ag⁺ to EDTA, the molar ratio of water to surfactant (ω₀), and the aging time.     

Preparation of water dispersible,fluorescent Ag–PAA–PVP hybrid nanogels and their optical properties

A simple method of synthesizing hybrid silver–polyacrylic acid–poly(N-vinylpyrrolidone) (Ag–PAA–PVP) nanogels was demonstrated through in situ reducing Ag⁺ inside PAA–PVP nanogels, which were formed by polymerization of acrylic acid in the PVP solution. Due to the ion exchange between Ag⁺ and acid protons of PAA, stable Ag⁺ clusters were formed inside the PAA–PVP nanogels, and hybrid nanogels were obtained by reducing Ag⁺ by ascorbic acid. Transmission electronic microscopic (TEM) images clearly showed the existence of silver nanoparticles inside the Ag–PAA–PVP nanogels. These hybrid nanogels showed typical surface plasma resonance absorption peak around 420 nm, and the size of the silver nanoparticles inside the Ag–PAA–PVP nanogels could be controlled from 9.5 ± 1.6 nm to 1.9 ± 0.4 nm by increasing the feeding amount of Ag⁺. In addition, these hybrid nanogels showed photoluminescent properties in fluorescent spectra. Considering the pH sensitive property of these hybrid nanogels, they will have potential application in drug delivery and biomedical imaging systems.     

Visible‐Light‐Induced Self‐Organized Helical Superstructure in Orientationally Ordered Fluids

Light‐induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible‐light‐induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible‐light‐driven chiral molecular switch. The cyclic‐azobenzene‐based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n–π* transitions of its trans‐ and cis‐isomers. Green light (530 nm) drives the trans‐to‐cis photoisomerization whereas the cis‐to‐trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light‐induced helical superstructure enables the formation of diffraction gratings in cholesteric films.