Oussama Zenasni

Superhydrophobic perfluorinated metal-organic frameworks.

Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

Simultaneous Chemical and Refractive Index Sensing in the 1-2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks.

Near-infrared (NIR) absorption spectroscopy provides molecular and chemical information based on overtones and combination bands of the fundamental vibrational modes in the infrared wavelengths. However, the sensitivity of NIR absorption measurement is limited by the generally weak absorption and the relatively poor detector performance compared to other wavelength ranges. To overcome these barriers, we have developed a novel technique to simultaneously obtain chemical and refractive index sensing in 1-2.5 μm NIR wavelength range on nanoporous gold (NPG) disks, which feature high-density plasmonic hot-spots of localized electric field enhancement. For the first time, surface-enhanced near-infrared absorption (SENIRA) spectroscopy has been demonstrated for high sensitivity chemical detection. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼10(4) has been demonstrated for the first C-H combination band at 2400 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time. The performance of this technique has been evaluated using various hydrocarbon compounds and crude oil samples.

Biosensing Using Magnetic Particle Detection Techniques

Magnetic particles are widely used as signal labels in a variety of biological sensing applications, such as molecular detection and related strategies that rely on ligand-receptor binding. In this review, we explore the fundamental concepts involved in designing magnetic particles for biosensing applications and the techniques used to detect them. First, we briefly describe the magnetic properties that are important for bio-sensing applications and highlight the associated key parameters (such as the starting materials, size, functionalization methods, and bio-conjugation strategies). Subsequently, we focus on magnetic sensing applications that utilize several types of magnetic detection techniques: spintronic sensors, nuclear magnetic resonance (NMR) sensors, superconducting quantum interference devices (SQUIDs), sensors based on the atomic magnetometer (AM), and others. From the studies reported, we note that the size of the MPs is one of the most important factors in choosing a sensing technique.

Bidentate Aromatic Thiols on Gold: New Insight Regarding the Influence of Branching on the Structure, Packing, Wetting, and Stability of Self-Assembled Monolayers on Gold Surfaces

A series of 2-phenylpropane-1,3-dithiol derivatives with single (R1ArDT), double (R2ArDT), and triple (R3ArDT) octadecyloxy chains substituted at the 4-, 3,5-, and, 3,4,5-positions, respectively, on the aromatic ring were synthesized and used to form self-assembled monolayers (SAMs) on gold. Insight into the relationship between the surface chain and headgroup packing densities was investigated by varying the number of surface chains for the bidentate adsorbates in these monolayers. Characterization of the resulting SAMs using ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry revealed that the tailgroups become more comformationally ordered and more densely packed as the number of alkyl chains per adsorbate was increased. Conversely, the molecular packing density (i.e., number of molecules per unit area) decreased as the number of alkyl chains per adsorbate was increased. Of particular interest, the desorption profiles obtained in isooctane at 80 °C suggested that the bidentate adsorbate with the most densely packed alkyl chains, R3ArDT, was significantly more stable than the other SAMs, producing the following relative order for thermal stability for the dithiolate SAMs: R3ArDT > R2ArDT > R1ArDT.

Catalytic assembly of DNA nanostructures on a nanoporous gold array as 3D architectures for label-free telomerase activity sensing

Telomerase, an enzyme known to catalyze telomere elongation by adding TTAGGG [thymine (T), adenine (A), and guanine (G)] repeats to the end of telomeres, is vital for cell proliferation. Overexpression of telomerase has been found in most tumor cells, resulting in telomere dysfunction and uncontrolled cellular proliferation. Thus, telomerase has been considered as a potential cancer biomarker, as well as a potential target in cancer therapy. In this study, telomerase-catalyzed growth of tandem G-quadruplex (G4) assembled on a nanoporous gold array (NPGA) resulted in the formation of three-dimensional hybrid nanoarchitectures. The generated nanostructure then captured malachite green (MG) (reporter molecule) without the need of a complicated labeling process. Upon laser irradiation, the captured MG molecules produced a surface-enhanced Raman scattering (SERS) signal that was generated by an abundant amount of plasmonic hot spots in the NPGA substrates. A limit of detection (LOD) of 10-10 IU along with a linear range, which was 3 orders of magnitude, was achieved, which was equivalent to the telomerase amount extracted from 20 HeLa cells. The LOD is 2 orders of magnitude better than that of the commercial enzyme-linked immunosorbent assay (ELISA), and it approaches that of the most sensitive technique, telomeric repeat amplification protocols (TRAP), which require a laborious and equipment-intensive polymerase chain reaction (PCR). In addition, X-ray photoelectron spectroscopy (XPS) was used to chemically identify and quantify the telomerase activity on the sensitized NPGA surface. Furthermore, the sensor was applied to screen the effectiveness of anti-telomerase drugs such as zidovudine, thus demonstrating the potential use of the sensor in telomerase-based diagnosis and drug development. Moreover, the framework represents a novel paradigm of collaborative plasmonic intensification and catalytic multiplication (c-PI/CM) for label-free biosensing.

Hydrophilic surfaces via the self-assembly of nitrile-terminated alkanethiols on gold

A series of CN-terminated alkanethiols were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The SAMs were characterized using ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The SAMs were compared to those derived from a series of analogous CH 3 -terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH 3 -terminated SAMs, which was largely due to their greater tilt angle on the surface. Additionally, the CN-terminated SAMs form well-ordered films on flat gold surfaces with relative packing densities being indistinguishable from the CH 3 -terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH 3 -terminated adsorbates, which was attributed to the dipole moment of the terminal group as well as the lone pair of the nitrogen atom of the CN-terminal group.

Quaternary Ammonium-Terminated Films Formed from Mixed Bidentate Adsorbates Provide a High-Capacity Platform for Oligonucleotide Delivery

The exposure of quaternary ammonium groups on surfaces allows self-assembled monolayers (SAMs) to serve as architectural platforms for immobilizing oligonucleotides. The current study describes the preparation of SAMs derived from four unique bidentate adsorbates containing two different ammonium termini (i.e., trimethyl- and triethyl-) and comparison to their monodentate analogs. Our studies found that SAMs derived from the bidentate adsorbates offered considerable enhancements in oligonucleotide binding when compared to SAMs derived from their monodentate analogs. The generated SAMs were analyzed using ellipsometry, X-ray photoelectron spectroscopy, contact angle goniometry, polarization modulation infrared reflection-absorption spectroscopy, and electrochemical quartz crystal microbalance. These analyses showed that the immobilization of oligonucleotides was affected by changes in the terminal functionalities and the relative packing densities of the monolayers. In efforts to enhance further the immobilization of oligonucleotides on these SAM surfaces, we explored the use of adsorbates having aliphatic linkers with systematically varying chain lengths to form binary SAMs on gold. Mixed monolayers with 50:50 ratios of adsorbates showed the greatest oligonucleotide binding. These studies lay the groundwork for oligonucleotide delivery using gold-based nanoparticles and nanoshells.

Monitoring adsorption of gold nanoparticles on gold nanodisk array using dark-field hyperspectral microscopy (Conference Presentation)

Localized surface plasmon resonance (LSPR) arises from the interaction of light with noble metal nanoparticles, which induces a collective oscillation in the free electrons. The size and shape of the metallic nanostructure significantly impact LSPR frequency and strength. Nanoplasmonic sensor has become a recent research focus due to its significant signal enhancement and robust signal transduction measured by extinction spectroscopy, fluorescence, Raman scattering, and absorption spectroscopy. Dark-field microscopy, in contrast, reports the scattered photons after light-matter interactions. In this case, the nanoparticles can be understood as dipole radiators whose free electrons oscillate in concert. Coupled with spectroscopy, this platform allows the collection of plasmonically scattered spectra from gold nanoparticles. Plasmonic coupling between electron-beam lithography patterned gold nanodisks (AuND) and colloidal gold nanoparticles (AuNP) can change the plasmonic resonance of the original entities, and can be effectively studied by dark-field hyperspectral microscopy. Typically, a pronounced redshift can be observed when plasmonic coupling occurs. When these nano-entities are functionalized with interactive surface moieties, biochemistry and molecular processes can be studied. In this paper, we will present the capability of assessing the process of immobilizing streptavidin-functionalized AuNPs on an array of biotin-terminated AuNDs. By monitoring changes in the LSPR band of AuNDs, we are able to evaluate similar processes in other molecular systems. In addition, plasmon coupling induced scattering intensity variations can be measured by an electron-multiplied charge-coupled device camera for rapid in situ monitoring. This method can potentially be useful in studying dynamic biophysical and biochemical processes in situ.