Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution.

We report herein a versatile and user-friendly synthetic methodology based on sequential functionalization that enables the synthesis of previously unknown perylene bisimide (PBI) dyes with up to five different substituents attached to the perylene core (e.g., compound 15). The key to the success of our strategy is a highly efficient regiospecific 7-mono- and 7,12-di-phenoxy bay substitution at the "imide-activated" 7- and 12-bay positions of 1,6,7,12-tetrachloroperylene monoimide diester 1. The facile subsequent conversion of the diester groups into an imide group resulted in novel PBIs (e.g., compound 14) with two phenoxy substituents specifically at the 7- and 12-bay positions. This conversion led to the activation of C-1 and C-6 bay positions, and thereafter, the remaining two chlorine atoms were substituted to obtain tetraphenoxy-PBI (compound 15) that has two different imide and three different bay substituents. The methodology provides excellent control over the functionalization pattern, which enables the synthesis of various regioisomeric pairs bearing the same bay substituents. Another important feature of this strategy is the high sensitivity of HOMO-LUMO energies and photoinduced charge transfer toward sequential functionalization. As a result, systematic fluorescence on-off switching has been demonstrated upon subsequent substitution with the electron-donating 4-methoxyphenoxy substituent.

Functionalized Anion-Exchange Membranes Facilitate Electrodialysis of Citrate and Phosphate from Model Dairy Wastewater.

In this study, the preparation of a new, functional anion-exchange membrane (AEM), containing guanidinium groups as the anion-exchanging sites (Gu-100), is described as well as the membrane characterization by XPS, water uptake, permselectivities, and electrical resistances. The functional membrane was also employed in pH-dependent electrodialysis experiments using model dairy wastewater streams. The properties of the new membrane are compared to those of a commercially available anion-exchange membrane bearing conventional quaternary ammonium groups (Gu-0). Guanidinium was chosen for its specific binding properties toward oxyanions: e.g., phosphate. This functional moiety was covalently coupled to an acrylate monomer via a facile two-step synthesis to yield bulk-modified membranes upon polymerization. Significant differences were observed in the electrodialysis experiments for Gu-0 and Gu-100 at pH 7, showing an enhanced phosphate and citrate transport for Gu-100 in comparison to Gu-0. At pH 10 the difference is much more pronounced: for Gu-0 membranes almost no phosphate and citrate transport could be detected, while the Gu-100 membranes transported both ions significantly. We conclude that having guanidinium groups as anion-exchange sites improves the selectivity of AEMs. As the presented monomer synthesis strategy is modular, we consider the implementation of functional groups into a polymer-based membrane via the synthesis of tailor-made monomers as an important step toward selective ion transport, which is relevant for various fields, including water treatment processes and fuel cells.

A Low-Power MEMS IDE Capacitor with Integrated Microhotplate: Application as Methanol Sensor using a Metal-Organic Framework Coating as Affinity Layer.

Capacitors made of interdigitated electrodes (IDEs) as a transducer platform for the sensing of volatile organic compounds (VOCs) have advantages due to their lower power operation and fabrication using standard micro-fabrication techniques. Integrating a micro-electromechanical system (MEMS), such as a microhotplate with IDE capacitor, further allows study of the temperature- dependent sensing response of VOCs. In this paper, the design, fabrication, and characterization of a low-power MEMS microhotplate with IDE capacitor to study the temperature-dependent sensing response to methanol using Zeolitic imidazolate framework (ZIF-8), a class of metal-organic framework (MOF), is presented. A Titanium nitride (TiN) microhotplate with aluminum IDEs suspended on a silicon nitride membrane is fabricated and characterized. The power consumption of the ZIF-8 MOF-coated device at an operating temperature of 50 ∘ C is 4.5 mW and at 200 ∘ C it is 26 mW. A calibration methodology for the effects of temperature of the isolation layer between the microhotplate electrodes and the capacitor IDEs is developed. The device coated with ZIF-8 MOF shows a response to methanol in the concentration range of 500 ppm to 7000 ppm. The detection limit of the sensor for methanol vapor at 20 ∘ C is 100 ppm. In situ study of sensing properties of ZIF-8 MOF to methanol in the temperature range from 20 ∘ C to 50 ∘ C using the integrated microhotplate and IDE capacitor is presented. The kinetics of temperature-dependent adsorption and desorption of methanol by ZIF-8 MOF are fitted with double-exponential models. With the increase in temperature from 20 ∘ C to 50 ∘ C, the response time for sensing of methanol vapor concentration of 5000 ppm decreases by 28%, whereas the recovery time decreases by 70%.

Fused Silica Microcapillaries Used for a Simple Miniaturization of the Electrified Liquid-Liquid Interface.

Short pieces of fused silica capillary tubing were used to support an electrified liquid-liquid interface. A methyl deactivated silica capillary having a diameter of 25 µm was filled with 1,2-dichloroethane solution and served as the organic part of the liquid-liquid interface. A nondeactivated fused silica capillary having a diameter of 5, 10, or 25 µm was filled with an aqueous HCl solution and served as the aqueous part of the electrochemical cell. For the latter, silanization of the capillary interior with chlorotrimethylsilane allowed for a successful phase reversal. All capillaries were characterized by ion transfer voltammetry using tetramethylammonium cation as a model ion. This simple, fast, and low-cost miniaturization technique was successfully applied for detection of the antibiotic ofloxacin.

Electrified Soft Interface as a Selective Sensor for Cocaine Detection in Street Samples.

A straightforward, direct, and selective method is presented for electrochemical cocaine identification in street samples. The sensing mechanism is based on a simple ion transfer reaction across the polarized liquid-liquid interface. The interfacial behavior of a number of cutting agents is also reported. Interfacial miniaturization has led to improved electroanalytical properties of the liquid-liquid interface based sensor as compared with the macroscopic analogue. The reported method holds great potential to replace colorimetric tests with poor selectivity for on-site street sample analysis.

A Molecular Level Approach To Elucidate the Supramolecular Packing of Light-Harvesting Antenna Systems.

The molecular geometry and supramolecular packing of two bichromophoric prototypic light harvesting compounds D1A2 and D2A2, consisting of two naphthylimide energy donors that were attached to the 1,7 bay positions of a perylene monoimide diester energy acceptor, have been determined by a hybrid approach using magic angle spinning NMR spectroscopy and electron nano-crystallography (ENC), followed by modelling. NMR shift constraints, combined with the P 1 ‾ space group obtained from ENC, were used to generate a centrosymmetric dimer of truncated perylene fragments. This racemic packing motif is used in a biased molecular replacement approach to generate a partial 3D electrostatic scattering potential map. Resolving the structure of the bay substituents is guided by the inversion symmetry, and the distance constraints obtained from heteronuclear correlation spectra. The antenna molecules form a pseudocrystalline lattice of antiparallel centrosymmetric dimers with pockets of partially disordered bay substituents. The two molecules in a unit cell form a butterfly-type arrangement. The hybrid methodology that has been developed is robust and widely applicable for critical structural underpinning of self-assembling structures of large organic molecules.

Fast and controlled fabrication of porous graphene oxide: application of AFM tapping for mechano-chemistry.

This paper describes a novel method to fabricate porous graphene oxide (PGO) from GO by exposure to oxygen plasma. Compared to other methods to fabricate PGO described so far, e.g. the thermal and steam etching methods, oxygen plasma etching method is much faster. We studied the development of the porosity with exposure time using atomic force microscopy (AFM). It was found that the development of PGO upon oxygen-plasma exposure can be controlled by tapping mode AFM scanning using a Si tip. AFM tapping stalls the growth of pores upon further plasma exposure at a level that coincides with the fraction of sp2 carbons in the GO starting material. We suggest that AFM tapping procedure changes the bond structure of the intermediate PGO structure, and these stabilized PGO structures cannot be further etched by oxygen plasma. This constitutes the first report of tapping AFM as a tool for local mechano-chemistry.

Metal-Organic Polyhedra-Coated Si Nanowires for the Sensitive Detection of Trace Explosives.

Surface-modified silicon nanowire-based field-effect transistors (SiNW-FETs) have proven to be a promising platform for molecular recognition in miniature sensors. In this work, we present a novel nanoFET device for the sensitive and selective detection of explosives based on affinity layers of metal-organic polyhedra (MOPs). The judicious selection of the geometric and electronic characteristics of the assembly units (organic ligands and unsaturated metal site) embedded within the MOP cage allowed for the formation of multiple charge-transfer (CT) interactions to facilitate the selective explosive inclusion. Meanwhile, the host-stabilized CT complex inside the cage acted as an effective molecular gating element to strongly modulate the electrical conductance of the silicon nanowires. By grafting the MOP cages onto a SiNW-FET device, the resulting sensor showed a good electrical sensing capability to various explosives, especially 2,4,6-trinitrotoluene (TNT), with a detection limit below the nanomolar level. Importantly, coupling MOPs-which have tunable structures and properties-to SiNW-based devices may open up new avenues for a wide range of sensing applications, addressing various target analytes.

Sensitive and Reversible Detection of Methanol and Water Vapor by In Situ Electrochemically Grown CuBTC MOFs on Interdigitated Electrodes.

The in situ electrochemical growth of Cu benzene-1,3,5-tricarboxylate (CuBTC) metal-organic frameworks, as an affinity layer, directly on custom-fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5-7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6-8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion-controlled kinetics (k = 2.9 mmol s-0.5 g-1CuBTC ). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity Ke = 174.8 bar-1 . A volume fraction fMeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu-IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100-8000 ppm.

The effect of guanidinium functionalization on the structural properties and anion affinity of polyelectrolyte multilayers.

Poly(allylamine hydrochloride) (PAH) is chemically functionalized with guanidinium (Gu) moieties in water at room temperature. The resulting PAH-Gu is used to prepare polyelectrolyte multilayers (PEMs) with poly(sodium 4-styrene sulfonate) (PSS) via layer-by-layer deposition. The polyelectrolyte (PE) adsorption processes are monitored real-time by optical reflectometry and a quartz crystal microbalance with dissipation monitoring (QCM-D). Compared to the reference PSS/PAH PEMs, the PSS/PAH-Gu PEMs show a lower amount of deposited PE materials, lower wet thickness, higher stability under alkaline conditions and higher rigidity. These differences are rationalized by the additional Gu-SO3(-) interactions, also affecting the conformation of the PE chains in the PEM. The interactions between the PEMs and various sodium salts (NaCl, NaNO3, Na2SO4 and NaH2PO4) are also monitored using QCM-D. From the changes in the frequency, dissipation responses and supportive Reflection Absorption Infrared Spectroscopy it is concluded that Gu-functionalized PEMs absorb more H2PO4(-) compared to the Gu-free reference PEMs. This can be understood by strong interactions between Gu and H2PO4(-), the differences in the anion hydration energy and the anion valency. It is anticipated that compounds like the presented Gu-functionalized PE may facilitate the further development of H2PO4(-) sensors and ion separation/recovery systems.

Ionophore-containing siloprene membranes: direct comparison between conventional ion-selective electrodes and silicon nanowire-based field-effect transistors.

Siloprene-based, ion-selective membranes (ISMs) were drop-casted onto a field-effect transistor device that consisted of a single-chip array of top-down prepared silicon nanowires (SiNWs). Within one array, two sets of SiNWs were covered with ISMs, each containing two different ionophores, allowing the simultaneous sensing of K and Na ions using a flow cell. It is shown that both ions can be effectively detected in the same solution over a wide concentration range from 10(-4) to 10(-1) M without interference. The ISMs were also analyzed in a conventional ISE configuration, allowing a direct comparison. While the responses for K(+) were similar for both sensor configurations, remarkably, the Na(+) response of the ISM-covered SiNW device was found to be higher than the one of the ISE configuration. The addition of a Na(+) buffering hydrogel layer between the SiO2 of the SiNW and the ISM reduced the response, showing the importance of keeping the boundary potential at the SiO2/ISM interface constant. The responses of the siloprene-covered SiNW devices were found to be stable over a period of at least 6 weeks, showing their potential as a multichannel sensor device.

Protein detection on biotin-derivatized polyallylamine by optical microring resonators.

Silicon optical microring resonators (MRRs) are sensitive devices that can be used for biosensing. We present a novel biosensing platform based on the application of polyelectrolyte (PE) layers on such MRRs. The top PE layer was covalently labeled with biotin to ensure binding sites for antibodies via a streptavidin-biotin binding scheme. Monitoring the shift in the microring resonance wavelength allows real-time, highly sensitive detection of the biomolecular interaction.

Synthesis of regioisomerically pure 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid derivatives.

The perylene derivative 1,7-dibromoperylene-3,4,9,10-tetracarboxylic tetrabutylester has been obtained in regioisomerically pure form, by employing a highly efficient, scalable, and robust synthesis starting from commercially available perylene-3,4,9,10-tetracarboxylic bisanhydride. Subsequently, this compound is utilized for the synthesis of extremely valuable and versatile regioisomerically pure intermediates, namely, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dibutylester monoanhydride, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic bisanhydride, and 1,7-dibromoperylene monoimid monoanhydride. These compounds possess at least one anhydride functionality in addition to the 1,7 bromo substituents and thus allow for a virtually limitless attachment of substituents both at the "peri" and the "bay" positions. The intermediate 1,7-dibromoperylene monoimide monoanhydride is of special interest as it provides access to unsymmetrically imide-substituted 1,7-dibromoperylene derivatives, which are not accessible by previously known procedures. Finally, substitution of the 1,7 bromine atoms in the bay area by phenoxy groups, which is a generally applied reaction for 1,7-dibromoperylene bisimides, was proven to be equally effective for a 1,7-dibromoperylene tetraester and a 1,7-dibromoperylene diester monoimid.

Lactate biosensors: current status and outlook.

Many research efforts over the last few decades have been devoted to sensing lactate as an important analytical target in clinical care, sport medicine, and food processing. Therefore, research in designing lactate sensors is no longer in its infancy and now is more directed toward viable sensors for direct applications. In this review, we provide an overview of the most immediate and relevant developments toward this end, and we discuss and assess common transduction approaches. Further, we critically describe the pros and cons of current commercial lactate sensors and envision how future sensing design may benefit from emerging new technologies.

Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces.

4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2-7 nm, which indicate multilayer formation. Decreasing the diazonium salt concentration and the reaction time resulted in a smaller layer thickness, but did not prevent the formation of multilayers. It was demonstrated, mainly by X-ray photoelectron spectroscopy (XPS), that the diazonium salts not only react with the H-terminated Si surface, but also with electrografted phenyl groups via azo-bond formation. These azo bonds can be electrochemically reduced at Ered = -1.5 V, leading to the corresponding amino groups. This reduction resulted in a modest decrease in layer thickness, and did not yield monolayers. This indicates that other coupling reactions, notably a biphenyl coupling, induced by electrochemically produced phenyl radicals, take place as well. In addition to the azo functionalities, the nitro functionalities in electrografted layers of 4-NBD were independently reduced to amino functionalities at a lower potential (Ered = -2.1 V). The presence of amino functionalities on fully reduced layers, both from 4-NBD- and 4-BBD-modified Si, was shown by the presence of fluorine after reaction with trifluoroacetic anhydride (TFAA). This study shows that the electrochemical reduction of azo bonds generates amino functionalities on layers produced by electrografting of aryldiazonium derivatives. In this way multifunctional layers can be formed by employing functional aryldiazonium salts, which is believed to be very practical in the fabrication of sensor platforms, including those made of multi-array silicon nanowires.

Influence of conductivity and dielectric constant of water-dioxane mixtures on the electrical response of SiNW-based FETs.

In this study, we report on the electrical response of top-down, p-type silicon nanowire field-effect transistors exposed to water and mixtures of water and dioxane. First, the capacitive coupling of the back gate and the liquid gate via an Ag/AgCl electrode were compared in water. It was found that for liquid gating smaller potentials are needed to obtain similar responses of the nanowire compared to back gating. In the case of back gating, the applied potential couples through the buried oxide layer, indicating that the associated capacitance dominates all other capacitances involved during this mode of operation. Next, the devices were exposed to mixtures of water and dioxane to study the effect of these mixtures on the device characteristics, including the threshold voltage (V(T)). The V(T) dependency on the mixture composition was found to be related to the decreased dissociation of the surface silanol groups and the conductivity of the mixture used. This latter was confirmed by experiments with constant conductivity and varying water-dioxane mixtures.

Robust fabrication method for silicon nanowire field effect transistors for sensing applications.

This paper demonstrates a new method for the top-down production of silicon nanowire field effect transistors for sensing applications. A simple and robust method for the fabrication of these devices is described, using only conventional CMOS (Complementary Metal Oxide Semiconductor) processing techniques making it manufacturable on large scale in a broad range of production facilities. Moreover, the process is flexible in terms of the choice of the type of front oxide of the transistor, as it is applied in a separate, independent step from the application of the surrounding oxide. In case ultimate small dimensions are required that go beyond the wafer stepper resolution, the use of e-beam technology to produce even smaller structures can be easily integrated. Furthermore, the use of a passivation layer opens possibilities for adding selectivity via surface modification on silicon dioxide and silicon. After a detailed description of the process, the electrical characteristics of the devices are shown together with data on the device reliability, indicating that the process is easy to manufacture, has a large yield and results in sensor devices with electrical characteristics in the desired regime.

Silicon nanowire-based devices for gas-phase sensing.

Since their introduction in 2001, SiNW-based sensor devices have attracted considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species. Most studies focus on detecting, sensing and monitoring analytes in aqueous solution, but the number of studies on sensing gases and vapors using SiNW-based devices is increasing. This review gives an overview of selected research papers related to the application of electrical SiNW-based devices in the gas phase that have been reported over the past 10 years. Special attention is given to surface modification strategies and the sensing principles involved. In addition, future steps and technological challenges in this field are addressed.

Nonaqueous Interfacial Polymerization-Derived Polyphosphazene Films for Sieving or Blocking Hydrogen Gas.

A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.4 × 10-17 cm3 cm cm-2 s-1 Pa-1 for hydrogen and 1.1 × 10-16 cm3 cm cm-2 s-1 Pa-1 for oxygen. For films obtained with a lower concentration of potassium hydroxide, single gas permeation experiments reveal a molecular sieving behavior, with a hydrogen permeance of around 10-8 mol m-2 s-1 Pa-1 and permselectivities of H2/N2 (52.8), H2/CH4 (100), and H2/CO2 (10.1) at 200 °C.

Comprehensive review on surfactant adsorption on mineral surfaces in chemical enhanced oil recovery.

With the increasing demand for efficient extraction of residual oil, enhanced oil recovery (EOR) offers prospects for producing more reservoirs' original oil in place. As one of the most promising methods, chemical EOR (cEOR) is the process of injecting chemicals (polymers, alkalis, and surfactants) into reservoirs. However, the main issue that influences the recovery efficiency in surfactant flooding of cEOR is surfactant losses through adsorption to the reservoir rocks. This review focuses on the key issue of surfactant adsorption in cEOR and addresses major concerns regarding surfactant adsorption processes. We first describe the adsorption behavior of surfactants with particular emphasis on adsorption mechanisms, isotherms, kinetics, thermodynamics, and adsorption structures. Factors that affect surfactant adsorption such as surfactant characteristics, solution chemistry, rock mineralogy, and temperature were discussed systematically. To minimize surfactant adsorption, the chemical additives of alkalis, polymers, nanoparticles, co-solvents, and ionic liquids are highlighted as well as implementing with salinity gradient and low salinity water flooding strategies. Finally, current trends and future challenges related to the harsh conditions in surfactant based EOR are outlined. It is expected to provide solid knowledge to understand surfactant adsorption involved in cEOR and contribute to improved flooding strategies with reduced surfactant loss.