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With the rapidly increasing demands for ultrasensitive biodetection, the design and applications of new nano-scale materials for development of sensors based on optical and electrochemical transducers have attracted substantial interest. In particular, given the comparable sizes of nanomaterials and biomolecules, there exist plenty of opportunities to develop functional nanoprobes with biomolecules for highly sensitive and selective biosensing, shedding new light on cellular behaviour. Towards this aim, herein we interface cells with patterned nano-arrays of carbon nanofibers forming a nanosensor-cell construct. We show that such a construct is capable of electrochemically communicating with the intracellular environment.

Herein, we report a highly sensitive electrocatalytic sensor-cell construct that can electrochemically communicate with the internal environment of immune cells (e.g., macrophages) via the selective monitoring of a particular reactive oxygen species (ROS), hydrogen peroxide. The sensor, which is based on vertically aligned single-walled carbon nanotubes functionalized with an osmium electrocatalyst, enabled the unprecedented detection of a local intracellular “pulse” of ROS on a short second time scale in response to bacterial endotoxin (lipopolysaccharide-LPS) stimulation. Our studies have shown that this initial pulse of ROS is dependent on NADPH oxidase (NOX) and toll like receptor 4 (TLR4). The results suggest that bacteria can induce a rapid intracellular pulse of ROS in macrophages that initiates the classical innate immune response of these cells to infection.

The fabrication of a molecularly tailored surface functionalised with a saccharide binding motif, a phenyl boronic acid derivative is reported.The functionalised surface facilitated the transfer of electrons, via unique electronic interactions mediated by the presence of the boronic acid, from a macrophage cell line. This is the first example of eukaryotic cellular-electrical communication mediated by the binding of cells via their cell–surface saccharide units.

Since glycoproteins have become increasingly recognized as key players in a wide variety of disease processes, there is an increasing need for advanced affinity materials for highly selective glycoprotein binding. Herein, for the first time, a surface-initiated controlled radical polymerization is integrated with supramolecular templating and molecular imprinting to yield highly reproducible synthetic recognition sites on surfaces with dissociation constants (KDs) in the low micromolar range for target glycoproteins and minimal binding to non-target glycoproteins. Importantly, it is shown that the synthetic strategy has remarkable ability to distinguish the glycosylated and non-glycosylated forms of the same glycoprotein, with >5-fold difference in binding affinity. The precise control over the polymer film thickness and positioning of multiple carbohydrate receptors plays a crucial role in achieving enhanced affinity and selectivity. The generated functional materials of unprecedented glycoprotein recognition performance open up a wealth of opportunities in the biotechnological and biomedical fields.

Self-assembled monolayers (SAMs) containing azobenzene moieties are very attractive for a wide range of applications, including molecular electronics and photonics, bio-interface engineering and sensoring. However, very little is known about the aggregation and photoswitching behavior that azobenzene units undergo during the SAM formation process. Here, we demonstrate that the formation of thiol based SAMs containing azobenzenes (denoted as AzoSH) on gold surfaces is characterised by a two step adsorption kinetics, while a three-step assembly process has been identified for dithiolane-based SAMs containing azobenzenes (denoted AzoSS). The H-aggregation on the AzoSS SAMs was found to be remarkably dependent on the time of self-assembly, with less aggregation as a function of time. While photoisomerization of the AzoSH was suppressed for all different assembly times, the reversible trans–cis photoisomerization of AzoSS SAMs formed over 24 hours was clearly observed upon alternating UV and Vis light irradiation. We contend that detailed information on formation kinetics and related optical properties is of crucial importance for elucidating the photoswitching capabilities of azobenzene based SAMs.

Gold is a standard surface for attachment of thiol-based self-assembled monolayers (SAMs). To achieve uniform defect free SAM coatings, which are essential for bio/chemical sensing applications, the gold surface must have low roughness, and be highly orientated. These requirements are normally achieved by either heating during Au deposition or post deposition Au surface annealing. This paper shows that room temperature deposited gold, can afford equivalent gold surfaces, if the gold deposition parameters are carefully controlled. This observation is an important result as heating (or annealing) of the deposited gold can have a detrimental effect on the mechanical properties of the silicon on which the gold is deposited used in microsensors. The paper presents the investigation of the morphology and crystalline structure of Au film prepared by thermal evaporation at room temperature on silicon. The effect of gold deposition rate is studied, and it is shown that by increasing the deposition rate from 0.02 nm s-1 to 0.14 nm s-1 the gold surface RMS roughness decreases, whereas the grain size of the deposited gold is seen to follow a step function decreasing suddenly between 0.06 and 0.10 nm s-1. The XRD intensity of the preferentially [111] orientated gold crystallites is also seen to increase as the deposition rate increases up to a deposition rate of 0.14 nm s-1. Formation and characterization of 1-dodecanethiol on these Au coated samples is also studied using contact angle. It is shown that by increasing the Au deposition rate the contact angle hysteresis (CAH) decreases until it plateaus, for a deposition rate greater than 0.14 nm s-1, where the CAH is smaller than 9 degrees which is an indication of homogeneous SAM formation, on a smooth surface.

Since glycoproteins have become increasingly recognized as key players in a wide variety of disease processes, there is an increasing need for advanced affinity materials for highly selective glycoprotein binding. Herein, for the first time, a surface-initiated controlled radical polymerization is integrated with supramolecular templating and molecular imprinting to yield highly reproducible synthetic recognition sites on surfaces with dissociation constants (KDs) in the low micromolar range for target glycoproteins and minimal binding to non-target glycoproteins. Importantly, it is shown that the synthetic strategy has remarkable ability to distinguish the glycosylated and non-glycosylated forms of the same glycoprotein, with >5-fold difference in binding affinity. The precise control over the polymer film thickness and positioning of multiple carbohydrate receptors plays a crucial role in achieving enhanced affinity and selectivity. The generated functional materials of unprecedented glycoprotein recognition performance open up a wealth of opportunities in the biotechnological and biomedical fields.

Self-assembled monolayers (SAMs) containing azobenzene moieties are very attractive for a wide range of applications, including molecular electronics and photonics, bio-interface engineering and sensoring. However, very little is known about the aggregation and photoswitching behavior that azobenzene units undergo during the SAM formation process. Here, we demonstrate that the formation of thiol based SAMs containing azobenzenes (denoted as AzoSH) on gold surfaces is characterised by a two step adsorption kinetics, while a three-step assembly process has been identified for dithiolane-based SAMs containing azobenzenes (denoted AzoSS). The H-aggregation on the AzoSS SAMs was found to be remarkably dependent on the time of self-assembly, with less aggregation as a function of time. While photoisomerization of the AzoSH was suppressed for all different assembly times, the reversible trans–cis photoisomerization of AzoSS SAMs formed over 24 hours was clearly observed upon alternating UV and Vis light irradiation. We contend that detailed information on formation kinetics and related optical properties is of crucial importance for elucidating the photoswitching capabilities of azobenzene based SAMs.

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

With the rapidly increasing demands for ultrasensitive biodetection, the design and applications of new nano-scale materials for development of sensors based on optical and electrochemical transducers have attracted substantial interest. In particular, given the comparable sizes of nanomaterials and biomolecules, there exist plenty of opportunities to develop functional nanoprobes with biomolecules for highly sensitive and selective biosensing, shedding new light on cellular behaviour. Towards this aim, herein we interface cells with patterned nano-arrays of carbon nanofibers forming a nanosensor-cell construct. We show that such a construct is capable of electrochemically communicating with the intracellular environment.

The fabrication of a molecularly tailored surface functionalised with a saccharide binding motif, a phenyl boronic acid derivative is reported.The functionalised surface facilitated the transfer of electrons, via unique electronic interactions mediated by the presence of the boronic acid, from a macrophage cell line. This is the first example of eukaryotic cellular-electrical communication mediated by the binding of cells via their cell–surface saccharide units.

Herein, we report a highly sensitive electrocatalytic sensor-cell construct that can electrochemically communicate with the internal environment of immune cells (e.g., macrophages) via the selective monitoring of a particular reactive oxygen species (ROS), hydrogen peroxide. The sensor, which is based on vertically aligned single-walled carbon nanotubes functionalized with an osmium electrocatalyst, enabled the unprecedented detection of a local intracellular “pulse” of ROS on a short second time scale in response to bacterial endotoxin (lipopolysaccharide-LPS) stimulation. Our studies have shown that this initial pulse of ROS is dependent on NADPH oxidase (NOX) and toll like receptor 4 (TLR4). The results suggest that bacteria can induce a rapid intracellular pulse of ROS in macrophages that initiates the classical innate immune response of these cells to infection.

Gold is a standard surface for attachment of thiol-based self-assembled monolayers (SAMs). To achieve uniform defect free SAM coatings, which are essential for bio/chemical sensing applications, the gold surface must have low roughness, and be highly orientated. These requirements are normally achieved by either heating during Au deposition or post deposition Au surface annealing. This paper shows that room temperature deposited gold, can afford equivalent gold surfaces, if the gold deposition parameters are carefully controlled. This observation is an important result as heating (or annealing) of the deposited gold can have a detrimental effect on the mechanical properties of the silicon on which the gold is deposited used in microsensors. The paper presents the investigation of the morphology and crystalline structure of Au film prepared by thermal evaporation at room temperature on silicon. The effect of gold deposition rate is studied, and it is shown that by increasing the deposition rate from 0.02 nm s-1 to 0.14 nm s-1 the gold surface RMS roughness decreases, whereas the grain size of the deposited gold is seen to follow a step function decreasing suddenly between 0.06 and 0.10 nm s-1. The XRD intensity of the preferentially [111] orientated gold crystallites is also seen to increase as the deposition rate increases up to a deposition rate of 0.14 nm s-1. Formation and characterization of 1-dodecanethiol on these Au coated samples is also studied using contact angle. It is shown that by increasing the Au deposition rate the contact angle hysteresis (CAH) decreases until it plateaus, for a deposition rate greater than 0.14 nm s-1, where the CAH is smaller than 9 degrees which is an indication of homogeneous SAM formation, on a smooth surface.

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

With the rapidly increasing demands for ultrasensitive biodetection, the design and applications of new nano-scale materials for development of sensors based on optical and electrochemical transducers have attracted substantial interest. In particular, given the comparable sizes of nanomaterials and biomolecules, there exist plenty of opportunities to develop functional nanoprobes with biomolecules for highly sensitive and selective biosensing, shedding new light on cellular behaviour. Towards this aim, herein we interface cells with patterned nano-arrays of carbon nanofibers forming a nanosensor-cell construct. We show that such a construct is capable of electrochemically communicating with the intracellular environment.

Herein, we report a highly sensitive electrocatalytic sensor-cell construct that can electrochemically communicate with the internal environment of immune cells (e.g., macrophages) via the selective monitoring of a particular reactive oxygen species (ROS), hydrogen peroxide. The sensor, which is based on vertically aligned single-walled carbon nanotubes functionalized with an osmium electrocatalyst, enabled the unprecedented detection of a local intracellular “pulse” of ROS on a short second time scale in response to bacterial endotoxin (lipopolysaccharide-LPS) stimulation. Our studies have shown that this initial pulse of ROS is dependent on NADPH oxidase (NOX) and toll like receptor 4 (TLR4). The results suggest that bacteria can induce a rapid intracellular pulse of ROS in macrophages that initiates the classical innate immune response of these cells to infection.

The fabrication of a molecularly tailored surface functionalised with a saccharide binding motif, a phenyl boronic acid derivative is reported.The functionalised surface facilitated the transfer of electrons, via unique electronic interactions mediated by the presence of the boronic acid, from a macrophage cell line. This is the first example of eukaryotic cellular-electrical communication mediated by the binding of cells via their cell–surface saccharide units.

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

With the rapidly increasing demands for ultrasensitive biodetection, the design and applications of new nano-scale materials for development of sensors based on optical and electrochemical transducers have attracted substantial interest. In particular, given the comparable sizes of nanomaterials and biomolecules, there exist plenty of opportunities to develop functional nanoprobes with biomolecules for highly sensitive and selective biosensing, shedding new light on cellular behaviour. Towards this aim, herein we interface cells with patterned nano-arrays of carbon nanofibers forming a nanosensor-cell construct. We show that such a construct is capable of electrochemically communicating with the intracellular environment.

The fabrication of a molecularly tailored surface functionalised with a saccharide binding motif, a phenyl boronic acid derivative is reported.The functionalised surface facilitated the transfer of electrons, via unique electronic interactions mediated by the presence of the boronic acid, from a macrophage cell line. This is the first example of eukaryotic cellular-electrical communication mediated by the binding of cells via their cell–surface saccharide units.

Herein, we report a highly sensitive electrocatalytic sensor-cell construct that can electrochemically communicate with the internal environment of immune cells (e.g., macrophages) via the selective monitoring of a particular reactive oxygen species (ROS), hydrogen peroxide. The sensor, which is based on vertically aligned single-walled carbon nanotubes functionalized with an osmium electrocatalyst, enabled the unprecedented detection of a local intracellular “pulse” of ROS on a short second time scale in response to bacterial endotoxin (lipopolysaccharide-LPS) stimulation. Our studies have shown that this initial pulse of ROS is dependent on NADPH oxidase (NOX) and toll like receptor 4 (TLR4). The results suggest that bacteria can induce a rapid intracellular pulse of ROS in macrophages that initiates the classical innate immune response of these cells to infection.