Biofouling, the adsorption of organisms to a surface, is a major problem today in many areas of our lives. This includes: (i) health, as biofouling on medical device leads to hospital-acquired infections, (ii) water, since the accumulation of organisms on membranes and pipes in desalination systems harms the function of the system, and (iii) energy, due to the heavy load of the organic layer that accumulates on marine vessels and causes a larger consumption of fuel. This paper presents an effective electrochemical approach for generating antifouling and antimicrobial surfaces. Distinct from previously reported antifouling or antimicrobial electrochemical studies, we demonstrate the formation of a hydrogen gas bubble layer through the application of a low-voltage square waveform pulses to the conductive surface. This electrochemically generated gas bubble layer serves as a separation barrier between the surroundings and the target surface where the adhesion of bacteria can be deterred. Our results indicate that this barrier could effectively reduce the adsorption of bacteria to the surface by 99.5%. We propose that the antimicrobial mechanism correlates with the fundamental of hydrogen evolution reaction (HER). HER leads to an arid environment that does not allow the existence of live bacteria. In addition, we show that this drought condition kills the preadhered bacteria on the surface due to water stress. This work serves as the basis for the exploration of future self-sustainable antifouling techniques such as incorporating it with photocatalytic and photoelectrochemical reactions.

The electrochemically triggered release of doxorubicin (DOX) from flexible electrodes modified electrophoretically with reduced graphene oxide (rGO)-DOX is reported. The release is driven by a positive potential pulse that decreases the pH of the rGO-DOX surface locally, which is confirmed by scanning electrochemical microscopy (SECM) in situ. In vitro cell viability tests confirms that the delivery system meets therapeutic needs.

A key component in solar thermal energy conversion system is the light collector that is coated with an absorbing material. Optimal performance is accomplished by high absorptance and low emittance. The best collectors are fabricated by vacuum deposition processes, which are limited to small size and flat objects. Here, the formation and performance of a new three-layer solar selective coating, which is formed by a simple wet-deposition process is reported. The solar absorbing layer is based on carbon nanotubes, which are considered the most absorbing material. This layer is coated by a second layer of ITO, which functions as an IR reflecting layer, followed by an AlOOH anti-reflective layer. The resulting CNT/ITO/AlOOH coating exhibited the best-reported spectral selectivity by wet deposition process, with high absorptance of 0.941 +/- 0.004 and low emittance of 0.13 +/- 0.02 at room temperature. Furthermore, the multilayer sprayable coating is stable at elevated temperature for a prolong time and therefore, shows promise for application in large scale and on-site solar thermal facilities.

A new redox-free electrochemical approach for driving the deposition of two-dimensional (2D) layered MoS2 nanosheets is described. First, poly(acylic acid) (PAA) functionalized layered MoS2 nanosheets (PAA-MoS2) is prepared to form a stable aqueous PAA-MoS2 dispersion, which is subsequently used for the electrochemical deposition. In contrast to previous electrodeposition methods of MoS2, which involve the redox of molecular precursors of Mo and S, herein we introduce an electrochemical approach for the deposition of 2D layered MoS2 nanosheets directly from their nanometric building blocks, namely from their aqueous dispersion. This ``nano to nano'' approach is based on altering the ionic strength at the vicinity of the electrode surface by applying a potential. Specifically, the electrogeneration of Cue-1 ions, cause the PAA-MoS2 nanosheets in the dispersion to aggregate and deposit on the copper electrode. Scanning electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy analysis show clearly that the deposited layered MoS2 maintains its original structure. Furthermore, the ;electrodeposited PAA-MoS2 nanosheets on copper show excellent catalytic activity for the hydrogen evolution reaction with low overpotential. Hence, we believe that these findings could lead to a generic approach for the formation of thin films or patterns of 2D nanomaterials. (C) 2017 Elsevier Ltd. All rights reserved.

Sensitive and selective detection of cancer biomarkers is vital for the successful diagnosis of early stage cancer and follow-up treatment. Surface Plasmon Resonance (SPR) in combination with different amplification strategies is one of the analytical approaches allowing the screening of protein biomarkers in serum. Here we describe the development of a point-of-care sensor for the detection of folic acid protein (FAP) using graphene-based SPR chips. The exceptional properties of CVD graphene were exploited to construct a highly sensitive and selective SPR chip for folate biomarker sensing in serum. The specific recognition of FAP is based on the interaction between folic acid receptors integrated through pi-stacking on the graphene coated SPR chip and the FAP analyte in serum. A simple post-adsorption of human serum:bovine serum albumin (HS:BSA) mixtures onto the folic acid modified sensor resulted in a highly anti-fouling interface, while keeping the sensing capabilities for folate biomarkers. This sensor allowed femtomolar (fM) detection of FAP, a detection limit well adapted and promising for quantitative clinical analysis. (C) 2016 Elsevier B.V. All rights reserved.

Molybdenum trioxide is an interesting inorganic system in which the empty 4d states have potential to hold extra electrons and therefore can change states from insulating opaque (MoO3) to colored semimetallic (HxMoO3). Here, we characterize the local electrogeneration and charge transfer of the synthetic layered two-dimensional 2D MoO3-II (a polymorph of MoO3 and analogous to alpha-MoO3) in response,to two different redox couples; i.e., [Ru(NH3)(6)](3+) and [Fe(CN)(6)](3-) by scanning electrochemical microscopy (SECM). We identify the reduction of [Ru(NH3)(6)](3+) to [Ru(NH3)(6)](2+) at the microelectrode that leads to the reduction of MoO3-11 to conducting blue-colored molybdenum bronze H MoO3. It is recognized that the dominant conduction of the charges occurred preferentially at the edges active sites of the sheets, as edges of the sheets are found to be more conducting. This yields positive feedback current when approaching the microelectrode toward 2D MoO3-II-coated electrode. In contrast, the [Fe(CN)(6)](4-), which is reduced from [Fe(CN)(6)](3-), is found unfavorable to reduce MoO3-II due to its higher redox potential, thus showing a negative feedback current. The charge transfer on MoO3-II is further studied as a function of applied potential. The results shed light on the charge transfer behavior on the surface of MoO3-II coatings and opens the possibility of locally tuning of their oxidation states.

Scanning electrochemical microscopy (SECM) offers an alternative approach for precise local electrodeposition of micro and nanometer structures driven by electrochemistry. The tip generation and substrate collection mode of SECM has been applied to deposit sub-micron palladium structures by using a Pd microelectrode. This was compared with a different approach based on scanning ion conductance microscopy (SICM). The latter was utilized also for the localized electrochemical deposition of Pd patterns using a pulled micropipette as a tip. The micropipette was filled with PdCl42- and biased versus a reference electrode placed in a NaCl solution. The application of a negative potential to the micropipette causes negatively charged ions, PdCl4-, to egress the pipette, which were electrochemically reduced on a conducting surface. The Pd patterns locally deposited by SECM and SICM were used for the local electroless deposition of Cu. Comparison between the two techniques shows that SICM is superior to SECM in terms of resolution and ease of tip preparation.

Post-surgery infections are considered the most challenging complication in the orthopedic and dental field. The local release of antibiotics is evidently highly efficient in delivering the drug to the vicinity of the infected area without the risk of systemic toxicity. Bioactive materials, such as hydroxyapatite (HAp) among other calcium phosphates, are reputed as superior antibiotic vehicles, and combine drug-delivery properties and enhanced osteoconductivity. Here, we report on the single-step electrophoretic deposition (EPD) of drug-loaded HAp nanoparticles (NPs) on titanium implants. This approach provides a purely bioactive coating with drug delivery properties in a simple, economic, and fast process. We synthesized pure HAp NPs with 12.5% and 12.8% loading weight percentages of gentamicin sulfate (Gs) and ciprofloxacin (Cip), and electrophoretically deposited them on a titanium substrate. Furthermore, we co-deposited Gs-HAp and Cip-HAp in one-step to yield a drug-loaded system consisting of two types of antibiotics. The drug- loaded NPs as well as the coatings were carefully characterized. The release profiles of the Gs-HAp and Cip-HAp NP coatings showed prolonged release of up to 10 and 25 days, respectively. The bioactivity test revealed superior bioactivity with enhanced precipitation of HAp crystals along with inorganic minerals, such as Mg2+, Na+, and Cl-. The antibacterial in vitro tests of the Cip and Gs-HAp coatings showed efficient inhibition of Pseudomonas aeruginosa bacteria.

An appealing alternative approach to the conventional electro-chemical deposition is presented, which can be universally utilized to form nanomaterial coatings from their aqueous dispersions without involving their oxidation-reduction. It is based on altering the ionic strength by electrical potential in the vicinity of the electrode surface, which causes the nanomaterials to deposit. The concept has been demonstrated for four different systems.

We report the first attempt of using molecularly imprinted polymers (MIPs) in the shape of nanoparticles that were doped with gold nanoparticles (AuNPs) for surface enhanced Raman scattering (SERS)-based sensing of molecular species. Specifically, AuNPs doped molecularly imprinted nano-spheres (AuNPs@nanoMIPs) were synthesized by one-pot precipitation polymerization using Sudan IV as the template for the SERS sensing. The AuNPs@nanoMIPs were characterized by various modes of scanning transmission electron microscopy (STEM) that showed the exact location of the AuNPs inside the MIP particles. The effects of Au concentration and solution stirring on the shape and the polydispersity of the particles were studied. Significant enhancement of the Raman signals was observed only when the MIP particles were doped with the AuNPs. The SERS signal improved significantly with increase in the Au concentration inside the AuNPs@nanoMIPs. Selectivity measurements of the Sudan IV imprinted AuNPs@nanoMIPs carried out with different Sudan derivatives showed high selectivity of the AuNPs-doped MIP particles.

Calcium phosphate (CaP) ceramics have been prevalently used as coatings for implants because of their excellent osteoconductive and bioactive properties. Yet, bone regeneration procedures might have complications such as bacterial infection, local inflammation, bone destruction, and impaired bone healing. Here, we present a novel in situ electrodeposition of CaP with chitosan nanoparticles containing antibiotics. The deposition was shown to be fast and efficient. The deposited layer of octacalcium phosphate (OCP) and monotite contained a large amount of gentamicin, which was released gradually over a period of 15 days. These phases may be beneficial for bone growth, as OCP has higher solubility than the stoichiometric hydroxyapatite (HAp) and is commonly considered as a precursor to HAp, while monotite has even faster resorbability. In addition, both the cytotoxicity and biomineralization of the coating were studied, and the coating was proven to be noncytotoxic and highly biomimetic.

An appealing alternative approach to the conventional electrochem. deposition is presented, which can be universally utilized to form nanomaterial coatings from their aq. dispersions without involving their oxidn.-redn. It is based on altering the ionic strength by elec. potential in the vicinity of the electrode surface, which causes the nanomaterials to deposit. The concept has been demonstrated for four different systems. [on SciFinder(R)]

We report the first attempt of using molecularly imprinted polymers (MIPs) in the shape of nanoparticles that were doped with gold nanoparticles (AuNPs) for surface enhanced Raman scattering (SERS)-based sensing of mol. species. Specifically, AuNPs doped molecularly imprinted nano-spheres (AuNPs@nanoMIPs) were synthesized by one-pot pptn. polymn. using Sudan IV as the template for the SERS sensing. The AuNPs@nanoMIPs were characterized by various modes of scanning transmission electron microscopy (STEM) that showed the exact location of the AuNPs inside the MIP particles. The effects of Au concn. and soln. stirring on the shape and the polydispersity of the particles were studied. Significant enhancement of the Raman signals was obsd. only when the MIP particles were doped with the AuNPs. The SERS signal improved significantly with increase in the Au concn. inside the AuNPs@nanoMIPs. Selectivity measurements of the Sudan IV imprinted AuNPs@nanoMIPs carried out with different Sudan derivs. showed high selectivity of the AuNPs-doped MIP particles. [Figure not available: see fulltext.]. [on SciFinder(R)]

Sensitive and selective detection of cancer biomarkers is vital for the successful diagnosis of early stage cancer and follow-up treatment. Surface Plasmon Resonance (SPR) in combination with different amplification strategies is one of the anal. approaches allowing the screening of protein biomarkers in serum. Here we describe the development of a point-of-care sensor for the detection of folic acid protein (FAP) using graphene-based SPR chips. The exceptional properties of CVD graphene were exploited to construct a highly sensitive and selective SPR chip for folate biomarker sensing in serum. The specific recognition of FAP is based on the interaction between folic acid receptors integrated through π-stacking on the graphene coated SPR chip and the FAP analyte in serum. A simple post-adsorption of human serum:bovine serum albumin (HS:BSA) mixts. onto the folic acid modified sensor resulted in a highly anti-fouling interface, while keeping the sensing capabilities for folate biomarkers. This sensor allowed femtomolar (fM) detection of FAP, a detection limit well adapted and promising for quant. clin. anal. [on SciFinder(R)]