Chemical and Photochemical-Driven Dissipative Fe3+/Fe2+-Ion Cross-Linked Carboxymethyl Cellulose Gels Operating Under Aerobic Conditions: Applications for Transient Controlled Release and Mechanical Actuation.

A Fe3+-ion cross-linked carboxymethyl cellulose, Fe3+-CMC, redox-active gel exhibiting dissipative, transient stiffness properties is introduced. Chemical or photosensitized reduction of the higher-stiffness Fe3+-CMC to the lower-stiffness Fe2+-CMC gel, accompanied by the aerobic reoxidation of the Fe2+-CMC matrix, leads to the dissipative, transient stiffness, functional matrix. The light-induced, temporal, transient release of a load (Texas red dextran) and the light-triggered, transient mechanical bending of a poly-N-isopropylacrylamide (p-NIPAM)/Fe3+-CMC bilayer construct are introduced, thus demonstrating the potential use of the dissipative Fe3+-CMC gel for controlled drug release or soft robotic applications.

Selective Deposition of N-Heterocyclic Carbene Monolayers on Designated Au Microelectrodes within an Electrode Array.

The incorporation of organic self-assembled monolayers (SAMs) in microelectronic devices requires precise spatial control over the self-assembly process. In this work, selective deposition of N-heterocyclic carbenes (NHCs) on specific electrodes within a two-microelectrode array is achieved by using pulsed electrodeposition. Spectroscopic analysis of the NHC-coated electrode arrays reveals that each electrode is selectively coated with a designated NHC. The impact of NHC monolayers on the electrodes' work function is quantified using Kelvin probe force microscopy. These measurements demonstrate that the work function values of each electrode can be independently tuned by the adsorption of a specific NHC. The presented deposition method enables to selectively coat designated microelectrodes in an electrode array with chosen NHC monolayers for tuning their chemical and electronic functionality.

Controlling the Surface of Aluminum Nanocrystals: From Aluminum Oxide to Aluminum Fluoride.

Aluminum nanocrystals are emerging as a promising alternative to silver and gold for various applications ranging from plasmonic functionalities to photocatalysis and as energetic materials. Such nanocrystals often exhibit an inherent surface oxidation layer, as aluminum is highly reactive. Its controlled removal is challenging but required, as it can hinder the properties of the encaged metal. Herein, two wet-chemical colloidal approaches toward the surface coating of Al nanocrystals, which afford control over the surface chemistry of the nanocrystals and the oxide thickness, are presented. The first approach utilizes oleic acid as a surface ligand by its addition toward the end of the Al nanocrystals synthesis, and the second approach is the post-synthesis treatment of Al nanocrystals with NOBF4 , in a "wet" colloidal-based approach, which is found to etch and fluorinate the surface oxides. As surface chemistry is an important handle for controlling materials' properties, this research paves a path for manipulating Al nanocrystals while promoting their utilization in diverse applications.

Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces.

N-heterocyclic carbenes (NHCs) have been widely utilized for the formation of self-assembled monolayers (SAMs) on various surfaces. The main methodologies for preparation of NHCs-based SAMs either requires inert atmosphere and strong base for deprotonation of imidazolium precursors or the use of specifically-synthesized precursors such as NHC(H)[HCO3] salts or NHC-CO2 adducts. Herein, we demonstrate an electrochemical approach for surface-anchoring of NHCs which overcomes the need for dry environment, addition of exogenous strong base or restricting synthetic steps. In the electrochemical deposition, water reduction reaction is used to generate high concentration of hydroxide ions in proximity to a metal electrode. Imidazolium cations were deprotonated by hydroxide ions, leading to carbenes formation that self-assembled on the electrode's surface. SAMs of NO2-functionalized NHCs and dimethyl-benzimidazole were electrochemically deposited on Au films. SAMs of NHCs were also electrochemically deposited on Pt, Pd and Ag films, demonstrating the wide metal scope of this deposition technique.

Symbolic emblems of the Levantine Aurignacians as a regional entity identifier (Hayonim Cave, Lower Galilee, Israel).

The Levantine Aurignacian is a unique phenomenon in the local Upper Paleolithic sequence, showing greater similarity to the West European classic Aurignacian than to the local Levantine archaeological entities preceding and following it. Herewith we highlight another unique characteristic of this entity, namely, the presence of symbolic objects in the form of notched bones (mostly gazelle scapulae) from the Aurignacian levels of Hayonim Cave, Lower Galilee, Israel. Through both macroscopic and microscopic analyses of the items, we suggest that they are not mere cut marks but rather are intentional (decorative?) human-made markings. The significance of this evidence for symbolic behavior is discussed in its chrono-cultural and geographical contexts. Notched bones are among the oldest symbolic expressions of anatomically modern humans. However, unlike other Paleolithic sites where such findings were reported in single numbers, the number of these items recovered at Hayonim Cave is sufficient to assume they possibly served as an emblem of the Levantine Aurignacian.

Boosting electrochemical water oxidation through replacement of Oh Co sites in cobalt oxide spinel with manganese.

The strikingly high catalytic performance and stability of manganese substituted cobalt oxide spinel (MnxCo3-xO4) over pristine cobalt oxide spinel (Co3O4) for the alkaline electrochemical water oxidation is reported. The different role of cations could be uncovered along with the detection of drastic surface-structural changes during the catalysis using spectroscopic and microscopic methods.

From a Molecular 2Fe-2Se Precursor to a Highly Efficient Iron Diselenide Electrocatalyst for Overall Water Splitting.

A highly active FeSe2 electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe-2Se precursor. The as-synthesized FeSe2 was electrophoretically deposited on nickel foam and applied to the oxygen and hydrogen evolution reactions (OER and HER, respectively) in alkaline media. When used as an oxygen-evolution electrode, a low 245 mV overpotential was achieved at a current density of 10 mA cm-2 , representing outstanding catalytic activity and stability because of Fe(OH)2 /FeOOH active sites formed at the surface of FeSe2 . Remarkably, the system is also favorable for the HER. Moreover, an overall water-splitting setup was fabricated using a two-electrode cell, which displayed a low cell voltage and high stability. In summary, the first iron selenide material is reported that can be used as a bifunctional electrocatalyst for the OER and HER, as well as overall water splitting.

Continuous thermal control of hydrophilicity/hydrophobicity changes of hybrid films and of their directionality: Kinetics and substrate effects.

A successful methodology for obtaining hybrid films which allow thermal triggering and continuous, irreversible, control of their hydrophilicity/hydrophobicity nature was developed. Two types of poly(dimethylsiloxane)-silica (PDMS@SiO2) films were prepared for that purpose: A hydrophilic film in which the thermal treatment causes an irreversible gradual increase of hydrophobicity; and a hydrophobic film that turns more hydrophilic upon thermal treatment. The opposite directionality of the change is dictated by the film substrate, on which the same hybrid is deposited. In both cases the thermal treatment induced a phase separation which caused the change in hydrophobicity. The magnitude of change in hydrophilicity/hydrophobicity is continuously controllable in both types of films by either the temperature or heating time. The films were characterized before and after heating by a variety of methods, including contact angle (CA) measurements with the sessile drop and the tilting plate methods, and by X-ray photoelectron spectroscopy (XPS) analysis. A thorough kinetic study was carried out, following the progress of the changes in the wettability property of the surfaces. The kinetics analyses proved that the changes in the wettability in all cases are due to phase separation processes, the directionality of which is determined by the treatment of the substrate on which the films are deposited. By monitoring the change of wettability (ΔCA) at various temperatures, an Arrhenius plot was obtained from which the activation energy and Arrhenius pre-exponential factor for the phase separation were derived, corroborating the proposed mechanism. To the best of our knowledge, this is the first use of phase separation behavior of a hybrid film in order to apply irreversible, thermally controllable change of surface wettability, tailored to proceed in opposite directions, and the first kinetic study of such a process.

Mimicking Horseradish Peroxidase Functions Using Cu2+-Modified Carbon Nitride Nanoparticles or Cu2+-Modified Carbon Dots as Heterogeneous Catalysts.

Cu2+-functionalized carbon nitride nanoparticles (Cu2+-g-C3N4 NPs), ∼200 nm, and Cu2+-carbon dots (Cu2+-C-dots), ∼8 nm, act as horseradish peroxidase-mimicking catalysts. The nanoparticles catalyze the generation of chemiluminescence in the presence of luminol/H2O2 and catalyze the oxidation of dopamine by H2O2 to form aminochrome. The Cu2+-g-C3N4-driven generation of chemiluminescence is used to develop a H2O2 sensor and is implemented to develop a glucose detection platform and a sensor for probing glucose oxidase. Also, the Cu2+-C-dots are functionalized with the ß-cyclodextrin (ß-CD) receptor units. The concentration of dopamine, at the Cu2+-C-dots' surface, by means of the ß-CD receptor sites, leads to a 4-fold enhancement in the oxidation of dopamine by H2O2 to yield aminochrome compared to that of the unmodified C-dots.

DNA-Metalization: Synthesis and Properties of Novel Silver-Containing DNA Molecules (Adv. Mater. 24/2016).

D. Porath, A. Kotlyar, and co-workers transform DNA to a conducting material by metalization through coating or chemical modifications, as described on page 4839. Specific and reversible metalization of poly(dG)-poly(dC) DNA by migration of atoms from silver nanoparticles to the DNA is demonstrated. As the transformation occurs gradually, novel, truly hybrid molecular structures are obtained, paving the way to their usage as nanowires in programmable molecular electronic devices and circuits.

A Transitional Gundi (Rodentia: Ctenodactylidae) from the Miocene of Israel.

We describe a new species of gundi (Rodentia: Ctenodactylidae: Ctenodactylinae), Sayimys negevensis, on the basis of cheek teeth from the Early Miocene of the Rotem Basin, southern Israel. The Rotem ctenodactylid differs from all known ctenodactylid species, including Sayimys intermedius, which was first described from the Middle Miocene of Saudi Arabia. Instead, it most resembles Sayimys baskini from the Early Miocene of Pakistan in characters of the m1-2 (e.g., the mesoflexid shorter than the metaflexid, the obliquely orientated hypolophid, and the presence of a strong posterolabial ledge) and the upper molars (e.g., the paraflexus that is longer than the metaflexus). However, morphological (e.g., presence of a well-developed paraflexus on unworn upper molars) and dimensional (regarding, in particular, the DP4 and M1 or M2) differences between the Rotem gundi and Sayimys baskini distinguish them and testify to the novelty and endemicity of the former. In its dental morphology, Sayimys negevensis sp. nov. shows a combination of both the ultimate apparition of key-characters and incipient features that would be maintained and strengthened in latter ctenodactylines. Thus, it is a pivotal species that bridges the gap between an array of primitive ctenodactylines and the most derived, Early Miocene and later, gundis.

Synthesis and Properties of Novel Silver-Containing DNA Molecules.

Migration of silver atoms from silver nano-particles selectively to a double-stranded poly(dG)-poly(dC) polymer leads to metallization of the DNA. As a result the DNA molecules become shorter and thicker (higher), as evident from the atomic force microscopy imaging analysis. The metalized molecules can be detected by transmission and scanning electron microscopy in contrast to the initial non-metalized ones.

Comparison of positive-pressure, passive ultrasonic, and laser-activated irrigations on smear-layer removal from the root canal surface.

OBJECTIVE: The purpose of this study was to compare the efficacy of three irrigation techniques for smear-layer removal with 17% EDTA. BACKGROUND DATA: Cleaning and shaping the root canal system during endodontic treatment produces a smear layer and hard tissue debris. Three irrigation techniques were tested for solution infiltration of this layer: positive-pressure irrigation, passive ultrasonic irrigation, and laser-activated irrigation. MATERIALS AND METHODS: Sixty extracted teeth were divided into six equal groups; 17% EDTA was used for 60 sec irrigation of five of the groups. The groups were as follows: Group 1, treated only with ProTaper™ F3 Ni-Ti files; Group 2, positive-pressure irrigation, with a syringe; Group 3, passive ultrasonic irrigation, inserted 1 mm short of the working length; Group 4, passive ultrasonic irrigation, inserted in the upper coronal third of the root; Group 5, Er:YAG laser-activated irrigation, inserted 1 mm short of the working length; and Group 6, Er:YAG laser-activated irrigation, inserted in the upper coronal third of the root. RESULTS: Scanning electron microscopy showed that the smear layer is removed most efficiently using laser-activated irrigation at low energy with 17% EDTA, inserted either at the working length or only in the coronal upper third of the root. Amounts of Ca, P, and O were not significantly different on all treated dentin surfaces. CONCLUSIONS: Smear-layer removal was most effective when the root canals were irrigated using Er:YAG laser at low energy with 17% EDTA solution. Interestingly, removal of the smear layer along the entire canal was similar when the laser was inserted in the upper coronal third and at 1 mm short of the working length of the root canal. This effect was not observed with the ultrasonic and positive-pressure techniques.

Using nickel manganese oxide catalysts for efficient water oxidation.

Nickel-manganese oxides with variable Ni : Mn ratios, synthesised from heterobimetallic single-source precursors, turned out to be efficient water oxidation catalysts. They were subjected to oxidant-driven, photo- and electro-catalytic water oxidation showing superior activity and remarkable stability. In addition, a structure-activity relation could be established.

Probing the interaction of individual amino acids with inorganic surfaces using atomic force spectroscopy.

This article describes single-molecule force spectroscopy measurements of the interaction between individual amino acid residues and inorganic surfaces in an aqueous solution. In each measurement, there is an amino acid residue, lysine, glutamate, phenylalanine, leucine, or glutamine, and each represents a class of amino acids (positively or negatively charged, aromatic, nonpolar, and polar). Force-distance curves measured the interaction of the individual amino acid bound to a silicon atomic force microscope (AFM) tip with a silcon substrate, cut from a single-crystal wafer, or mica. Using this method, we were able to measure low adhesion forces (below 300 pN) and could clearly determine the strength of interactions between the individual amino acid residues and the inorganic substrate. In addition, we observed how changes in the pH and ionic strength of the solution affected the adsorption of the residues to the substrates. Our results pinpoint the important role of hydrophobic interactions among the amino acids and the substrate, where hydrophobic phenylalanine exhibited the strongest adhesion to a silicon substrate. Additionally, electrostatic interactions also contributed to the adsorption of amino acid residues to inorganic substrates. A change in the pH or ionic strength values of the buffer altered the strength of interactions among the amino acids and the substrate. We concluded that the interplay between the hydrophobic forces and electrostatic interactions will determine the strength of adsorption among the amino acids and the surface. Overall, these results contribute to our understanding of the interaction at the organic-inorganic interface. These results may have implications for our perception of the specificity of peptide binding to inorganic surfaces. Consequently, it would possibly lead to a better design of composite materials and devices.

Effect of Er:YAG laser-activated irrigation solution on Enterococcus Faecalis biofilm in an ex-vivo root canal model.

UNLABELLED: Abstract Objective: The purpose of this study was to evaluate mineral content and surface morphology of root canals coated with Enterococcus faecalis biofilm after treatment with several endodontic irrigation solutions, with and without Er:YAG laser-activated irrigation (LAI). BACKGROUND DATA: LAI has been introduced as a powerful method for root canal irrigation resulting in smear-layer removal from the root canal wall. METHODS: Distal and palatal roots from 60 freshly extracted human molars were used in this study. The coronal of each tooth was removed. Roots were split longitudinally and placed in an ultrasonic bath to remove the smear layer, creating conditions for the formation of E. faecalis biofilm. After incubation, the two halves were reassembled in impression material to simulate clinical conditions. Specimens were divided into two main groups: roots rinsed with irrigation solutions and roots subjected to laser irradiation combined with irrigation solutions. Solutions tested were 2% chlorhexidine and 17% ethylenediaminetetraacetic acid (EDTA) and saline. RESULTS: Surface morphology: 17% EDTA irrigant solution combined with Er:YAG laser showed the best results for removing bacteria from the root canal walls. Chemical analysis: all samples treated with combined laser irradiation and irrigation solution had low surface levels of Ca compared with samples treated with irrigation alone. The Ca/P ratio was highest in the laser-EDTA group. Overall, mineral changes caused by laser with irrigation solutions were minimal, and statistically nonsignificant. CONCLUSIONS: In vitro irrigation solutions, combined with Er:YAG laser irradiation, were effective in removing E. faecalis biofilm from root canal walls. Irrigation solutions without laser irradiation were less effective, leaving a layer of biofilm on the dentin surface.

Preparation and characterization of mono- and multilayer films of polymerizable 1,2-polybutadiene using the Langmuir-Blodgett technique.

The essence of this study is to apply the Langmuir-Blodgett (LB) technique for assembling asymmetric membranes. Accordingly, Langmuir films of a (further) polymerizable polymer, 1,2-polybutadiene (1,2-pbd), were studied and transferred onto different solid supports, such as gold, indium tin oxide (ITO), and silicon. The layers were characterized both at the air/water interface as well as on different substrates using numerous methods including cyclic voltammetry, impedance spectroscopy, spectroscopic ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and reflection-absorption Fourier transform infrared spectroscopy. The Langmuir films were stable at the air-water interface as long as they were not exposed to UV irradiation. The LB films formed disorganized layers, which gradually blocked the permeation of different species with increasing the number of deposited layers. The thickness was ca. 4-7 Å per layer. Irradiating the Langmuir films caused their cross-linking at the air-water interface. Furthermore, we took advantage of the reactivity of the double bond of the LB films on the solid supports and graft polymerized acrylic acid on top of the 1,2-pbd layers. This approach is the basis of the formation of an asymmetric membrane that requires different porosity on both of its sides.

Effect of CPP-ACP and APF on Streptococcus mutans biofilm: A laboratory study.

PURPOSES: (1) To determine the effect of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) and acidulated phosphate fluoride (APF) on S. mutans viability, (2) to observe their effects on biofilm structure, and (3) to examine the element content of the hydroxyapatite (HA) surfaces after exposure to CPP-ACP and APF. METHODS: HA discs were coated with: CPP-ACP (GC Tooth-Mousse), APF, CPP-ACP+APF (1/1). Uncoated HA discs were used as control. Following application of the materials, the discs were immersed in human saliva and incubated with S. mutans ATCC (27315) for 24 hours. Growth of bacteria on the discs was evaluated by microbial culturing methods. The structure of the biofilm was examined with confocal laser scanning microscope (CLSM). The change in element content of HA surfaces (without biofilm) was evaluated with energy-dispersive x-ray spectroscopy (EDS). The values were statistically analyzed using Kruskal-Wallis and Dunn's test. RESULTS: The total number of bacteria of APF and CPP-ACP+APF applied groups were found significantly lower than the control group (P< 0.05). All specimens showed similar microbial colonization structure. No statistically significant differences were observed in O, F, Na, P, Ca content on HA surfaces after exposure to the tested agents, although fluoride concentration of the APF treated HA surfaces were increased compared to CPP-ACP, CPP-ACP +APF.

Thin nanocomposite films of polyaniline/Au nanoparticles by the Langmuir-Blodgett technique.

The Langmuir-Blodgett (LB) method was used to deposit multilayers of polyaniline (PANI)- and mercaptoethanesulfonate (MES)-stabilized Au nanoparticles. The electrostatic interaction between the negatively charged nanoparticles in the subphase and the positively charged PANI at the air-water interface assisted the deposition of the nanocomposite film onto a solid support. These PANI/Au-NPs films were characterized using cyclic voltammetry, copper under potential deposition, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. We found that the nanocomposite layers were uniform and reproducible. The density of Au-NPs in the monolayer depended on the acidity of the subphase as well as on the nanoparticles concentration. Moreover, the Au-NPs extrude above the PANI and therefore could be used as nanoelectrodes for the underpotential deposition (UPD) of copper.

Electrochemical deposition-stripping analysis of molecules and proteins by online electrochemical flow cell/mass spectrometry.

A methodology for online preconcentration of analytes and their subsequent electrochemically induced delivery to an online electrospray mass spectrometer is introduced. The approach is based on electrodeposition of an active metallic layer, silver deposit in this particular case, subsequent specific accumulation of the target analyte by electrochemical or chemical means onto the active layer, and finally oxidative electrostripping of the conductive layer along with the supported analyte to an online mass spectrometer. We demonstrate the new concept by selective electrochemical deposition of homocysteine and other organothiols directly on the working electrode of a miniature flow cell. The same approach was extended to the conjugation of the target analyte (avidin as a test case) to a thiolated ligand (biotin in this case) that was electrodeposited on the silver coated surface. Electrostripping of the silver dissolves the target species and allows their delivery to an online ESI-MS. Furthermore, the dissolved silver ions promote ionization, and its characteristic isotopic pattern assists in the identification of the target analyte.