Novel anionic surfactant-modified chlorhexidine and its potent antimicrobial properties.

Chlorhexidine dodecyl sulfate (CHX-DS) was synthesized and characterized via single-crystal X-ray diffraction (SC-XRD), 1H nuclear magnetic resonance (NMR) spectroscopy, 1H nuclear Overhauser effect spectroscopy (NOESY), and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR). The solid-state structure, comprising a 1 : 2 stoichiometric ratio of chlorhexidine cations [C22H30Cl2N10]2+ to dodecyl sulfate anions [C12H25SO4]-, is the first report of chlorhexidine isolated with a surfactant. CHX-DS exhibits broad-spectrum antibacterial activity and demonstrates superior efficacy for reducing bacteria-generated volatile sulfur compounds (VSCs) as compared to chlorhexidine gluconate (CHG). The minimum inhibitory concentrations (MICs) of CHX-DS were 7.5, 2.5, 2.5, and 10 µM for S. enterica, E. coli, S. aureus, and S. mutans, respectively. Furthermore, MIC assays for E. coli and S. mutans demonstrate that CHX-DS and CHX exhibit a statistically significant efficacy enhancement in 2.5 µM treatment as compared to CHG. CHX-DS was incorporated into SBA-15, a mesoporous silica nanoparticle (MSN) framework, and its release was qualitatively measured via UV-vis in aqueous media, which suggests its potential as an advanced functional material for drug delivery applications.

Naringin@Metal-Organic Framework as a Multifunctional Bioplatform.

Naringin, a natural product, can be used as a therapeutic agent due to its low systemic toxicity and negligible adverse effect. However, due to its hydrophobic nature and thereby low solubility, high-dose treatment is required when used for human therapy. Herein, we demonstrate the employment of a metal-organic framework (MOF) as a nontoxic loading carrier to encapsulate naringin, and the afforded nairngin@MOF composite can serve as a multifunctional bioplatform capable of treating Gram-positive bacteria and certain cancers by slowly and progressively releasing the encapsulated naringin as well as improving and modulating immune system functions through synergy between naringin and the MOF.

Cetylpyridinium Trichlorostannate: Synthesis, Antimicrobial Properties, and Controlled-Release Properties via Electrical Resistance Tomography.

Cetylpyridinium trichlorostannate (CPC-Sn), comprising cetylpyridinium chloride (CPC) and stannous chloride, was synthesized and characterized via single-crystal X-ray diffraction measurements indicating stoichiometry of C21H38NSnCl3 where the molecules are arranged in a 1:1 ratio with a cetylpyridinium cation and a [SnCl3]- anion. CPC-Sn has shown potential for application as a broad-spectrum antimicrobial agent, to reduce bacteria-generated volatile sulfur compounds and to produce advanced functional materials. In order to investigate its controlled-release properties, electrical resistance tomography was implemented. The results demonstrate that CPC-Sn exhibits extended-release properties in an aqueous environment as opposed to the CPC counterpart.

Dual Roles of Polymeric Capping Ligands in the Surface-Protected Etching of Colloidal Silica.

In this work, we reveal the dual roles of polymeric capping ligands in the hollowing of silica nanospheres during their surface-protected etching. We first show that polymeric capping ligands, if they have a stronger interaction with the surface Si-OH groups than water, can reduce the condensation of the silica network, allowing the diffusion of OH- ions through the shell to dissolve the inner silica. Also, the polymeric ligands can passivate the surface silica, making it less likely to be dissolved by OH- ions. The combination of these two roles ensures highly selective etching of the interior of the colloidal silica spheres, making the surface-protected etching a robust process for the synthesis of hollow silica nanoshells. Our insight into the specific roles of the ligands is expected to elucidate the impact of polymeric ligands on the colloidal chemistry of silica, particularly in its condensation and etching behaviors, and offer new opportunities in the design of silica and other oxide-based nanostructures.

Synthesis, Characterization, and Investigation of the Antimicrobial Activity of Cetylpyridinium Tetrachlorozincate.

Cetylpyridinium tetrachlorozincate (referred to herein as (CP)2ZnCl4) was synthesized and its solid-state structure was elucidated via single-crystal X-ray diffraction (SC-XRD), revealing a stoichiometry of C42H76Cl4N2Zn with two cetylpyridinium (CP) cations per [ZnCl4]2- tetrahedra. Crystal structures at 100 and 298 K exhibited a zig-zag pattern with alternating alkyl chains and zinc units. The material showed potential for application as a broad-spectrum antimicrobial agent, to reduce volatile sulfur compounds (VSCs) generated by bacteria, and in the fabrication of advanced functional materials. Minimum inhibitory concentration (MIC) of (CP)2ZnCl4 was 60, 6, and 6 µg mL-1 for Salmonella enterica, Staphylococcus aureus, and Streptococcus mutans, respectively. The MIC values of (CP)2ZnCl4 were comparable to that of pure cetylpyridinium chloride (CPC), despite the fact that approximately 16% of the bactericidal CPC is replaced with bacteriostatic ZnCl2 in the structure. A modified layer-by-layer deposition technique was implemented to synthesize mesoporous silica (i.e., SBA-15) loaded with approximately 9.0 wt % CPC and 8.9 wt % Zn.

Synthesis, Characterization, and Antimicrobial Investigation of a Novel Chlorhexidine Cyclamate Complex.

The synthesis, crystal structure, and antimicrobial efficacy are reported for a novel material comprising a 1:2 ratio of chlorhexidine (CHX) to N-cyclohexylsulfamate (i.e., artificial sweetener known as cyclamate). The chemical structure is unambiguously identified by incorporating a combination of single-crystal X-ray diffraction (SC-XRD), electrospray ionization mass spectrometry (ESI-MS), 1H nuclear magnetic resonance (NMR) spectroscopy, correlation spectroscopy (COSY), and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR). The new material: 1) is amongst only several reported structures identified to date incorporating the vital chlorhexidine antimicrobial drug; 2) exhibits broad spectrum antimicrobial activity at concentrations less than 15 µg/mL; and 3) provides a unique delivery method for the essential active pharmaceutical ingredient (API). Furthermore, substitution of inactive gluconate with bioactive cyclamate counterion potentially provides the additional benefit of improving the taste profile of chlorhexidine.

Stabilization of cationic aluminum hydroxide clusters in high pH environments with a CaCl2/l-arginine matrix.

We present a way of stabilizing cationic partially hydrolyzed aluminum clusters in a non-acidic environment, through Ca2+ and l-Arginine doping. The Keggin Al13-mer (ε-AlO4Al12(OH)24(H2O)127+) aluminum cluster can be stabilized with CaCl2 and l-arginine in a way to preserve the metal clusters. We use size-exclusion chromatography (SEC) and 27Al nuclear magnetic resonance (NMR) spectroscopy to demonstrate that positively-charged Keggin structures are preserved and that the conversion to Al(OH)3 materials is halted even at alkaline pH. The system serves to stabilize acidic Al clusters in alkaline or neutral conditions, while preserving their inherent cationic behavior.

One-Pot Hydrothermal Synthesis of Benzalkonium-Templated Mesostructured Silica Antibacterial Agents.

Novel mesostructured silica microparticles are synthesized, characterized, and investigated as a drug delivery system (DDS) for antimicrobial applications. The materials exhibit a relatively high density (0.56 g per 1 g SiO2) of benzalkonium chloride (BAC), pore channels of 18 Å in width, and a high surface area (1500 m2/g). Comparison of the small-angle X-ray diffraction (SAXRD) pattern with Barrett-Joyner-Halenda (BJH) pore size distribution data suggests that the 18 Å pores exhibit short-range ordering and a wall thickness of ca. 12 Å. Drug release studies demonstrate pH-responsive controlled release of BAC without additional surface modification of the materials. Prolonged drug release data were analyzed using a power law (Korsmeyer-Peppas) model and indicate substantial differences in release mechanism in acidic (pH 4.0, 5.0, 6.5) versus neutral (pH 7.4) solutions. Microbiological assays demonstrate a significant time-dependent reduction in Staphylococcus aureus and Salmonella enterica viability above 10 and 130 mg L-1 of the synthesized materials, respectively. The viability of cells is reduced over time compared to control samples. The findings will help in widening the use of BAC as a disinfectant and bactericidal agent, especially in pharmaceutical and food industries where Gram-positive and Gram-negative bacterial contamination is common.

Hybrid Materials and Nanocomposites as Multifunctional Biomaterials.

This review article provides an overview of hybrid and nanocomposite materials used as biomaterials in nanomedicine, focusing on applications in controlled drug delivery, tissue engineering, biosensors and theranostic systems. Special emphasis is placed on the importance of tuning the properties of nanocomposites, which can be achieved by choosing appropriate synthetic methods and seeking synergy among different types of materials, particularly exploiting their nanoscale nature. The challenges in fabrication for the nanocomposites are highlighted by classifying them as those comprising solely inorganic phases (inorganic/inorganic hybrids), organic phases (organic/organic hybrids) and both types of phases (organic/inorganic hybrids). A variety of examples are given for applications from the recent literature, from which one may infer that significant developments for effective use of hybrid materials require a delicate balance among structure, biocompatibility, and stability.

Facile Preparation of Ultrafine Aluminum Hydroxide Particles with or without Mesoporous MCM-41 in Ambient Environments.

An aqueous suspension of nanogibbsite was synthesized via the titration of aluminum aqua acid [Al(H2O)6]3+ with L-arginine to pH 4.6. Since the hydrolysis of aqueous aluminum salts is known to produce a wide array of products with a wide range of size distributions, a variety of state-of-the-art instruments (i.e., 27Al/1H NMR, FTIR, ICP-OES, TEM-EDX, XPS, XRD, and BET) were used to characterize the synthesis products and identification of byproducts. The product, which was comprised of nanoparticles (10-30 nm), was isolated using gel permeation chromatography (GPC) column technique. Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) identified the purified material as the gibbsite polymorph of aluminum hydroxide. The addition of inorganic salts (e.g., NaCl) induced electrostatic destabilization of the suspension, thereby agglomerating the nanoparticles to yield Al(OH)3 precipitate with large particle sizes. By utilizing the novel synthetic method described here, Al(OH)3 was partially loaded inside the highly ordered mesoporous framework of MCM-41, with average pore dimensions of 2.7 nm, producing an aluminosilicate material with both octahedral and tetrahedral Al (Oh/Td = 1.4). The total Al content, measured using energy-dispersive X-ray spectrometry (EDX), was 11% w/w with a Si/Al molar ratio of 2.9. A comparison of bulk EDX with surface X-ray photoelectron spectroscopy (XPS) elemental analysis provided insight into the distribution of Al within the aluminosilicate material. Furthermore, a higher ratio of Si/Al was observed on the external surface (3.6) as compared to the bulk (2.9). Approximations of O/Al ratios suggest a higher concentration of Al(O)3 and Al(O)4 groups near the core and external surface, respectively. The newly developed synthesis of Al-MCM-41 yields a relatively high Al content while maintaining the integrity of the ordered silica framework and can be used for applications where hydrated or anhydrous Al2O3 nanoparticles are advantageous.