Krassimir N. Bozhilov

A New Solution for the Removal of the Smear Layer

Various organic acids, ultrasonic instruments, and lasers have been used to remove the smear layer from the surface of instrumented root canals. The purpose of this study was to investigate the effect of a mixture of a tetracycline isomer, an acid, and a detergent (MTAD) as a final rinse on the surface of instrumented root canals. Forty-eight extracted maxillary and mandibular single-rooted human teeth were prepared by using a combination of passive step-back and rotary 0.04 taper nickel-titanium files. Sterile distilled water or 5.25% sodium hypochlorite was used as intracanal irrigant. The canals were then treated with 5 ml of one of the following solutions as a final rinse: sterile distilled water, 5.25% sodium hypochlorite, 17% EDTA, or a new solution, MTAD. The presence or absence of smear layer and the amount of erosion on the surface of the root canal walls at the coronal, middle, and apical portion of each canal were examined under a scanning electron microscope. The results show that MTAD is an effective solution for the removal of the smear layer and does not significantly change the structure of the dentinal tubules when canals are irrigated with sodium hypochlorite and followed with a final rinse of MTAD.

Metal and silicate particles including nanoparticles are present in electronic cigarette cartomizer fluid and aerosol.

Background Electronic cigarettes (EC) deliver aerosol by heating fluid containing nicotine. Cartomizer EC combine the fluid chamber and heating element in a single unit. Because EC do not burn tobacco, they may be safer than conventional cigarettes. Their use is rapidly increasing worldwide with little prior testing of their aerosol. Objectives We tested the hypothesis that EC aerosol contains metals derived from various components in EC. Methods Cartomizer contents and aerosols were analyzed using light and electron microscopy, cytotoxicity testing, x-ray microanalysis, particle counting, and inductively coupled plasma optical emission spectrometry. Results The filament, a nickel-chromium wire, was coupled to a thicker copper wire coated with silver. The silver coating was sometimes missing. Four tin solder joints attached the wires to each other and coupled the copper/silver wire to the air tube and mouthpiece. All cartomizers had evidence of use before packaging (burn spots on the fibers and electrophoretic movement of fluid in the fibers). Fibers in two cartomizers had green deposits that contained copper. Centrifugation of the fibers produced large pellets containing tin. Tin particles and tin whiskers were identified in cartridge fluid and outer fibers. Cartomizer fluid with tin particles was cytotoxic in assays using human pulmonary fibroblasts. The aerosol contained particles >1 µm comprised of tin, silver, iron, nickel, aluminum, and silicate and nanoparticles (<100 nm) of tin, chromium and nickel. The concentrations of nine of eleven elements in EC aerosol were higher than or equal to the corresponding concentrations in conventional cigarette smoke. Many of the elements identified in EC aerosol are known to cause respiratory distress and disease. Conclusions The presence of metal and silicate particles in cartomizer aerosol demonstrates the need for improved quality control in EC design and manufacture and studies on how EC aerosol impacts the health of users and bystanders.

Active facets on titanium(III)-doped TiO2: an effective strategy to improve the visible-light photocatalytic activity.

The properties and applications of materials are significantly controlled by their physical characteristics, such as size, shape, and structural state. Many processes are governed by interface reactions by which the surface energy and reactivity depend on the spatial configuration, coordination, and structural state of surface atoms and molecules. For crystals, this dependence is directly related to the expression of specific crystallographic faces, which exhibit different surface structures and atomic configurations. These differences explain why some applications, such as molecular adsorption and desorption, gas sensing, drug molecule delivery and release, and heterogeneous catalysis are highly sensitive to the surface atomic structures. Recent progress in the engineering of crystal morphology has included the synthesis of polyhedral silver nanocrystals by the polyol method, the epitaxially seeded growth of highly faceted Pt-Pd nanocrystals, and the controlled overgrowth of Pd-Au core–shell structures enclosed by {111} facets. Apart from these metallic nanocrystals, binary or ternary compounds with preferentially developed facets have also been reported. The facet effect is an important factor for heterogeneous photocatalysts, because surface atom arrangement and coordination intrinsically determine the adsorption of reactant molecules, surface transfer between photoexcited electrons and reactant molecules, and desorption of product molecules. This phenomenon has been well studied in TiO2 photocatalysts. TiO2 is one of the most extensively studied photocatalysts owing to its abundance, nontoxicity, and stability. However, for practical applications, pure TiO2 is not a good candidate because it is only active under ultraviolet (UV) irradiation owing to the band gap of 3.2 eV for the anatase phase. Therefore, band-gap engineering is required to use TiO2 as a water-splitting catalyst under visible-light irradiation. Reduced TiO2 (TiO2 x), containing Ti or O vacancies, has been reported to show visible-light absorption. Various strategies have been applied to synthesize reduced TiO2, such as heating under vacuum [8] or reducing gas, laser irradiation, and high-energy particle bombardment (electrons or Ar ions). A big challenge for the application of reduced TiO2 is that the surface oxygen defects are highly unstable in air owing to the susceptibility of Ti toward oxidation by O2. [13] Recently, we reported a facile one-step combustion method to synthesize partially reduced TiO2. [14] The presence of Ti in the sample extends the photoresponse of TiO2 from the UV to the visible light region, which leads to high visible-light photocatalytic activity for the generation of hydrogen gas from water. However, in the rapid and harsh combustion process, there is very limited control over the crystallization process, which results in the irregularly shaped products. Herein we report the development of a simple solution method to grow non-stoichiometric rutile TiO2 crystals with desired facets. The incorporation of Ti, which extends the light absorption from the UV into the visible range, along with the development of facets with high reactivity, results in a material exhibiting greatly enhanced photocatalytic H2 production activity relative to the combustion product we reported before. Powder X-ray diffraction analysis (Figure 1a) shows that the sample of as-produced TiO2 (sample S1) has rutile structure. All of the diffraction peaks can be assigned to

Analysis of an ultra hard magnetic biomineral in chiton radular teeth

Recent analyses of the ultrastructural and mechanical properties of mineralized biological materials have demonstrated some common architectural features that can help explain their observed damage tolerance. Nature has accomplished this feat through the precise control of anisotropic crystal nucleation and growth processes in conjunction with nanoscale control over the self-assembly of spatially distinct organic and inorganic phases, resulting in effective inhibition of crack propagation through these materials. One such example is found in the hyper-mineralized and abrasion resistant radular teeth of the chitons, a group of herbivorous marine mollusks who have the surprising capacity to erode away the rocky substrates on which they graze 1-4 . Through the use of modern microscopy and nanomechanical characterization techniques, we describe the architectural and mechanical properties of the radular teeth from Cryptochiton stelleri. Chiton teeth are shown to exhibit the largest hardness and stiffness of any biominerals reported to date, being notably as much as three-fold harder than human enamel and the calcium carbonate-based shells of mollusks. We explain how the unique multi-phasic design of these materials contributes not only to their functionality, but also highlights some interesting design principles that might be applied to the fabrication of synthetic composites.

Investigation of the Physicochemical Changes Preceding Zeolite Nucleation in a Sodium-Rich Aluminosilicate Gel

All industrially available zeolites are obtained from hydrogel systems. Unfortunately the level of understanding of the events preceding zeolite crystallization is far from satisfactory. In this respect, revealing the nature of the processes taking place in the precursor gel is of paramount importance to understanding zeolite nucleation. The investigation of the gel structure, however, is a difficult task due to the complexity of the object in terms of both composition and topology. Therefore, a combination of hyperpolarized (HP) (129)Xe NMR-N(2) adsorption-high-resolution transmission electron microscopy-energy-dispersive spectrometry methods complemented by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, and chemical analyses has been employed to study the changes in composition and structure of sodium hydroxide rich aluminosilicate gel yielding zeolite A. The role of each component in the system and the entire sequence of events during the induction, nucleation, and crystallization stages have been revealed. The high concentration of sodium hydroxide in the studied system has been found to control the size and structure of the gel particles in the beginning stage. During the initial polymerization of aluminosilicate species a significant part of the sodium hydroxide is expelled from the gel into the solution, which restricts extensive polymerization and leads to formation of small aluminosilicate particles with open pore structure. The induction period that follows is marked by incorporation of Na back in the bulk gel. The combined action of the Na ion as a structure-directing agent and the hydroxyl group as a mobilizer results in partial depolymerization of the gel and formation of voids with mesopore sizes. The nucleation maximum coincides temporally with development of pores with sizes in the range of 2-5 nm. The amorphous gel undergoes into crystalline zeolite only after these pores have disappeared and the chemistry of the gel has evolved to reach the stoichiometric zeolite composition. It was established unambiguously by high-resolution transmission electron microscopy and HP (129)Xe NMR that the nucleation of zeolite occurs in the solid part of the system and the succeeding crystallization commences only after the nuclei are released into the liquid, which is consistent with the autocatalytic mechanism. Also this investigation has demonstrated the unrivaled sensitivity of HP (129)Xe NMR that is capable of identifying presence of small amounts of crystalline zeolite material in amorphous medium with detection limit extending below 1 wt %.

Peptide-mediated shape- and size-tunable synthesis of gold nanostructures.

While several biological processes have been shown to be useful for the production of well-designed, inorganic nanostructures, the mechanism(s) controlling the size and shape of nano and micron size particles remains elusive. Here we report on the controlled size- and shape-specific production of gold nanostructures under ambient reaction conditions using a dodecapeptide, Midas-2, originally selected from a phage-displayed combinatorial peptide library. Single amino acid changes in Midas-2 greatly influence the size (a few nanometers to approximately 100 microm) and shape (nanoparticles, nanoribbons, nanowires and nanoplatelets) of the gold nanostructures produced, and these are controllable by adjusting the solution pH and gold ion concentration. The ability to control the shape and size of the gold nanostructures by changing the peptide structure and reaction conditions will lead to many potential applications, including nanoelectronics, sensors and optoelectronics, because of their unique size- and shape-dependent optical and electrical properties.

Microbial Synthesis of CdS Nanocrystals in Genetically Engineered E. coli

Semiconductor nanocrystals have been shown to possess unique optical, electrical, and optoelectronic properties for a wide range of applications. In particular, the exploitation of semiconductor nanocrystals, often referred to as quantum dots, in biological applications has increased dramatically because of their unique spectral properties, which enable simultaneous multiplex labeling and detection. More importantly, the spectral properties of these semiconductor nanocrystals can be controlled effectively by tuning the size, composition, surface properties, and crystal structure of the nanocrystals. Conventional chemical synthesis based on high-temperature organometallic processes is extremely toxic and expensive, and involves unstable species. For practical purposes, an alternative “green chemistry” scheme that is safe, simple, inexpensive, and suitable for industrial upscaling is extremely attractive. One promising alternative to chemical synthesis is the use of biological templates for the synthesis of nanocrystals. Many different biological templates, including peptides, nucleotides, and fusion proteins, are known to act as capping agents to regulate the synthesis of CdS, CdSe, and CdTe. Biological templates not only guide the nucleation of inorganic materials, but also control the crystal structure and size, under aqueous and ambient conditions. Biological approaches to nanocrystal synthesis can also be extended to living biological systems. Peptides capable of nucleating nanocrystal growth were displayed on the surface of M13 bacteriophage; the genetically engineered phage promoted the synthesis of crystalline nanowires, while preserving the exquisite regulation of material composition, size, and shape. Furthermore, the fission yeast Schizosaccharomyces pombe (S. pombe) has been used to promote the synthesis of CdS nanocrystals. In response to cadmium toxicity, S. pombe synthesizes phytochelatins (PCs) with repeating gGlu-Cys units to trap cadmium as nontoxic complexes. This low-molecular-weight complex composed of only cadmium and PCs is then transported actively into the vacuole and converted into highmolecular-weight PC–Cd–S complexes by the incorporation of sulfide. This process results in the formation of nanocrystals. During the nucleation process, PCs serve as a binding template/nucleation site for the metal ions and stabilize the nanocrystal core against continued aggregation. Although S. pombe has the intrinsic ability to form semiconductor nanocrystals by storing the peptide–metal complex in the vacuole as a defense mechanism, the multicompartment requirement makes it difficult to control and fine-tune the properties of the nanocrystals produced. Prokaryotes, such as bacteria, are ideal for engineering the synthesis of nanocrystals with precisely tailored size and crystallinity because of their single-compartment property. Escherichia coli (E. coli) is of particular interest, as the genetic tools and cellular metabolisms associated with this bacterium are well understood. Therefore, the guided assembly of genetic traits necessary for nanocrystal synthesis is possible. A recent study demonstrated the biosynthesis of CdS nanocrystals in E. coli without any genetic modification. However, only samples cultured for 24 h were shown to produce CdS nanocrystals, for which a large distribution in size from 2–5 nm was observed. More importantly, the mechanism of nanocrystal synthesis was not elucidated, and only a small subset of strains was able to synthesize nanocrystals. Inspired by the PC-based detoxification mechanism of S. pombe and the ability of this microorganism to create CdS nanocrystals, we genetically modified E. coli to establish a generalized approach to CdS-nanocrystal synthesis on the basis of the PC-directed method. To explore the feasibility of using E. coli as a biofactory for the controlled synthesis of CdS nanocrystals, the E. coli strain JM109 was endowed with the ability to produce PCs by expressing SpPCS, the PC synthase of S. pombe. A feedbackdesensitized g-glutamylcysteine synthetase (GSHI*), which catalyzes the synthesis of the PC precursor glutathione (GSH), was cotransformed to enhance the level of PC synthesis 10-fold, as reported elsewhere. Cells designed to synthesize PCs were grown in an LB medium (lysogeny broth) containing the appropriate antibiotics; isopropyl-b-d1-thiogalactopyranoside (IPTG) and cadmium chloride were added during the early exponential growth to promote PC synthesis and cadmium binding. Sodium sulfide was added 3 h after the addition of cadmium chloride to induce the formation of CdS nanocrystals for an additional 1 h. The formation of PC-templated CdS was first suggested by SDSPAGE analysis. When the CdS luminescence was visualized [*] S. H. Kang, Prof. N. V. Myung, Prof. A. Mulchandani, Prof. W. Chen Department of Chemical and Environmental Engineering University of California, Riverside Bourns Hall A242, Riverside, CA 92521 (USA) Fax: (+1)951-827-5696 E-mail: wilfred@engr.ucr.edu

Framework Stabilization of Ge-Rich Zeolites via Postsynthesis Alumination

The use of organic structure directing agents in zeolite syntheses has dramatically extended the number of zeolite structure types during the past decades. However, for about 20% of all known zeolite structure types, the necessary postsynthesis elimination of organic templates by high-temperature combustion leads to structure collapse, where the particularly strongly affected are Ge-rich zeolites. Here, we present a treatment approach that leads to zeolite structure stabilization by postsynthetic isomorphous substitution of Al for Ge. An important advantage of this new method is that no preliminary elimination of the organic structure directing agent from zeolite pores is required; thus it can be applied to microporous materials that cannot withstand the high temperature combustion of organic templates. The experimental data unambiguously show that besides framework stabilization the postsynthesis treatment facilitates incorporation of active sites in the zeolite framework. The feasibility of this new approach is corroborated by alumination of a BEC-type material. The presented method is expected to broaden the practical utilization of many microporous materials by improving their thermal stability.

Biomolecularly capped uniformly sized nanocrystalline materials: glutathione-capped ZnS nanocrystals

Micro-organisms such as bacteria and yeasts form CdS to detoxify toxic cadmium ions. Frequently, CdS particles formed in yeasts and bacteria were found to be associated with specific biomolecules. It was later determined that these biomolecules were present at the surface of CdS. This coating caused a restriction in the growth of CdS particles and resulted in the formation of nanometre-sized semiconductors (NCs) that exhibited typical quantum confinement properties. Glutathione and related phytochelatin peptides were shown to be the biomolecules that capped CdS nanocrystallites synthesized by yeasts Candida glabrata and Schizosaccharomyces pombe. Although early studies showed the existence of specific biochemical pathways for the synthesis of biomolecularly capped CdS NCs, these NCs could be formed in vitro under appropriate conditions. We have recently shown that cysteine and cysteine-containing peptides such as glutathione and phytochelatins can be used in vitro to dictate the formation of discrete sizes of CdS and ZnS nanocrystals. We have evolved protocols for the synthesis of ZnS or CdS nanocrystals within a narrow size distribution range. These procedures involve three steps: (1) formation of metallo-complexes of cysteine or cysteine-containing peptides, (2) introduction of stoichiometric amounts of inorganic sulfide into the metallo-complexes to initiate the formation of nanocrystallites and finally (3) size-selective precipitation of NCs with ethanol in the presence of Na+. The resulting NCs were characterized by optical spectroscopy, high-resolution transmission electron microscopy (HRTEM), x-ray diffraction and electron diffraction. HRTEM showed that the diameter of the ZnS-glutathione nanocrystals was 3.45?0.5 nm. X-ray diffraction and electron diffraction analyses indicated ZnS-glutathione to be hexagonal. Photocatalytic studies suggest that glutathione-capped ZnS nanocrystals prepared by our procedure are highly efficient in degrading a test model compound.

Intertwined nanocarbon and manganese oxide hybrid foam for high-energy supercapacitors.

Rapid charging and discharging supercapacitors are promising alternative energy storage systems for applications such as portable electronics and electric vehicles. Integration of pseudocapacitive metal oxides with single-structured materials has received a lot of attention recently due to their superior electrochemical performance. In order to realize high energy-density supercapacitors, a simple and scalable method is developed to fabricate a graphene/MWNT/MnO2 nanowire (GMM) hybrid nanostructured foam, via a two-step process. The 3D few-layer graphene/MWNT (GM) architecture is grown on foamed metal foils (nickel foam) via ambient pressure chemical vapor deposition. Hydrothermally synthesized α-MnO2 nanowires are conformally coated onto the GM foam by a simple bath deposition. The as-prepared hierarchical GMM foam yields a monographical graphene foam conformally covered with an intertwined, densely packed CNT/MnO2 nanowire nanocomposite network. Symmetrical electrochemical capacitors (ECs) based on GMM foam electrodes show an extended operational voltage window of 1.6 V in aqueous electrolyte. A superior energy density of 391.7 Wh kg(-1) is obtained for the supercapacitor based on the GMM foam, which is much higher than ECs based on GM foam only (39.72 Wh kg(-1) ). A high specific capacitance (1108.79 F g(-1) ) and power density (799.84 kW kg(-1) ) are also achieved. Moreover, the great capacitance retention (97.94%) after 13 000 charge-discharge cycles and high current handability demonstrate the high stability of the electrodes of the supercapacitor. These excellent performances enable the innovative 3D hierarchical GMM foam to serve as EC electrodes, resulting in energy-storage devices with high stability and power density in neutral aqueous electrolyte.