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Two series of lactone-terminated alkanethiol adsorbates with five- and six-membered lactone groups, γ-COCnSH and δ-COCnSH (n = 11, 12), were synthesized and employed to create nanoscale self-assembled monolayers (SAMs) on gold substrates to mimic the properties of commercially available poly(lactic-co-glycolic acid) (PLGA) and poly(glycolic acid) (PGA) surfaces. 1H and 13C nuclear magnetic resonance (NMR) were employed to characterize the adsorbate molecules. The thicknesses of the corresponding self-assembled monolayers (SAMs) were evaluated by ellipsometry. The conformational characteristics of the SAMs were analyzed using polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS), with a focus on the C-H antisymmetric stretching vibrations of the alkyl spacers. To evaluate the packing densities of the monolayers, X-ray photoelectron spectroscopy (XPS) measurements were performed. Separately, contact angle measurements provided insights into the wettability of the surfaces. Remarkably, the contact angle data across a broad range of probe liquids for the γ-COC11SH and γ-COC12SH SAMs were consistently similar to each other and to the contact angle values of the PLGA surface, rather than to PGA. This finding suggests that the lactone-terminated SAMs investigated in this study effectively mimic nanoscale polyester surfaces, enabling the exploration of interfacial properties of polyesters in the absence of swelling and/or surface reconstruction phenomena.

MicroRNA (miRNA) has emerged as a promising alternative therapeutic treatment for cancer, but its delivery has been hindered by low cellular uptake and degradation during circulation. In this review, we discuss the various methods of delivering miRNA, including viral and non-viral delivery systems such as liposomes and nanoparticles. We also examine the use of nanoparticles for miRNA-based diagnostics. We focus specifically on non-viral delivery systems utilizing coinage metals in the form of nanoparticles and the use of self-assembled monolayers (SAMs) as a method of surface modification. We review the use of SAMs for the conjugation and delivery of small noncoding ribonucleic acid (ncRNA), particularly SAMs derived from positively charged adsorbates to generate charged surfaces that can interact electrostatically with negatively charged miRNA. We also discuss the effects of the cellular uptake of gold and other plasmonic nanoparticles, as well as the challenges associated with the degradation of oligonucleotides. Our review highlights the potential of SAM-based systems as versatile and robust tools for delivering miRNA and other RNAs in vitro and in vivo and the need for further research to address the challenges associated with miRNA delivery and diagnostics.

This paper describes the preparation and characterization of a new type of core–shell nanoparticle in which the structure consists of a hydrogel core encapsulated within a porous silver shell. The thermo-responsive hydrogel cores were prepared by surfactant-free emulsion polymerization of a selected mixture of N-isopropylacrylamide (NIPAM) and acrylic acid (AAc). The hydrogel cores were then encased within either a porous or complete silver shell for which the localized surface plasmon resonance (LSPR) extends from visible to near-infrared (NIR) wavelengths (i.e., λmax varies from 550 to 1050 nm, depending on the porosity), allowing for reversible contraction and swelling of the hydrogel via photothermal heating of the surrounding silver shell. Given that NIR light can pass through tissue, and the silver shell is porous, this system can serve as a platform for the smart delivery of payloads stored within the hydrogel core. The morphology and composition of the composite nanoparticles were characterized by SEM, TEM, and FTIR, respectively. UV–vis spectroscopy was used to characterize the optical properties.

Due to their good magnetic properties, excellent biocompatibility, and low price, magnetic iron oxide nanoparticles (IONPs) are the most commonly used magnetic nanomaterials and have been extensively explored in biomedical applications. Although magnetic IONPs can be used for a variety of applications in biomedicine, most practical applications require IONP-based platforms that can perform several tasks in parallel. Thus, appropriate engineering and integration of magnetic IONPs with different classes of organic and inorganic materials can produce multifunctional nanoplatforms that can perform several functions simultaneously, allowing their application in a broad spectrum of biomedical fields. This review article summarizes the fabrication of current composite nanoplatforms based on integration of magnetic IONPs with organic dyes, biomolecules (e.g., lipids, DNAs, aptamers, and antibodies), quantum dots, noble metal NPs, and stimuli-responsive polymers. We also highlight the recent technological advances achieved from such integrated multifunctional platforms and their potential use in biomedical applications, including dual-mode imaging for biomolecule detection, targeted drug delivery, photodynamic therapy, chemotherapy, and magnetic hyperthermia therapy.

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 CH3-terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH3-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 CH3-terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH3-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.

Magnetite (Fe3O4) nanoparticles (NPs) are attractive nanomaterials in the field of material science, chemistry, and physics because of their valuable properties, such as soft ferromagnetism, half-metallicity, and biocompatibility. Various structures of Fe3O4 NPs with different sizes, geometries, and nanoarchitectures have been synthesized, and the related properties have been studied with targets in multiple fields of applications, including biomedical devices, electronic devices, environmental solutions, and energy applications. Tailoring the sizes, geometries, magnetic properties, and functionalities is an important task that determines the performance of Fe3O4 NPs in many applications. Therefore, this review focuses on the crucial aspects of Fe3O4 NPs, including structures, synthesis, magnetic properties, and strategies for functionalization, which jointly determine the application performance of various Fe3O4 NP-based systems. We first summarize the recent advances in the synthesis of magnetite NPs with different sizes, morphologies, and magnetic properties. We also highlight the importance of synthetic factors in controlling the structures and properties of NPs, such as the uniformity of sizes, morphology, surfaces, and magnetic properties. Moreover, emerging applications using Fe3O4 NPs and their functionalized nanostructures are also highlighted with a focus on applications in biomedical technologies, biosensing, environmental remedies for water treatment, and energy storage and conversion devices.

This manuscript describes a new type of nanomaterial, namely superparamagnetic Au@Co nanochains with optical extinctions in the near infrared (NIR). The Au@Co nanochains were synthesized via a one-pot galvanic replacement route involving a redox-transmetalation process in aqueous medium, where Au salt was reduced to form Au shells on Co seed templates, affording hollow Au@Co nanochains. The Au shells serve not only as a protective coating for the Co nanochain cores, but also to give rise to the optical properties of these unique nanostructures. Importantly, these bifunctional, magneto-optical Au@Co nanochains combine the advantages of nanophotonics (extinction at ca. 900 nm) and nanomagnetism (superparamagnetism) and provide a potentially useful new nanoarchitecture for biomedical or catalytic applications that can benefit from both activation by light and manipulation using an external magnetic field.

Nanotechnology has greatly enhanced the field of medicine over the last decade. Within this field, advances in nanoparticle research have rendered them attractive candidates for drug delivery. Consequently, controlling the chemistry that occurs at the nanoparticle interface influences the efficiency of the drug-delivery system. In this review, we explore the role of coating materials, in the form of self-assembled monolayers (SAMs), in enhancing the interfacial properties of nanoparticles. We discuss how SAMs enhance the properties of particles, such as stability and dispersibility, as well as provide a platform for delivering biomolecules and other therapeutic agents. In addition, we describe recent methods for generating nanoparticles with targeted surface functionality using custom-designed SAMs. These functionalities offer marked advances to the three stages of a drug-delivery system: loading, delivery, and release of therapeutic molecules. A suitable functionalization strategy can provide a means for covalent or non-covalent immobilization of drug molecules. Moreover, a robust coating layer can aid the encapsulation of drug molecules and inhibit molecular degradation during the delivery process. A stimuli-responsive SAM layer can also provide an efficient release mechanism. Thus, we also review how stimuli-responsive coatings allow for the controlled release of therapeutic agents. In addition, we discuss the merits and limitations of stimuli-responsive SAMs as well as possible strategies for future delivery systems. Overall, advances in this research area allow for developing novel drug delivery methodologies with high efficiency and minimal toxicity.

This article details the preparation of hollow gold-silver nanoshells (GS-NSs) coated with tunably thin silica shells for use in plasmon-enhanced photocatalytic applications. Hollow GS-NSs were synthesized via the galvanic replacement of silver nanoparticles. The localized surface plasmon resonance (LSPR) peaks of the GS-NSs were tuned over the range of visible light to near-infrared (NIR) wavelengths by adjusting the ratio of silver nanoparticles to gold salt solution to obtain three distinct types of GS-NSs with LSPR peaks centered near 500, 700, and 900 nm. Varying concentrations of (3-aminopropyl)trimethoxysilane and sodium silicate solution afforded silica shell coatings of controllable thicknesses on the GS-NS cores. For each type of GS-NS, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images verified our ability to grow thin silica shells having three different thicknesses of silica shell (~2, ~10, and ~15 nm) on the GS-NS cores. Additionally, energy-dispersive X-ray (EDX) spectra confirmed the successful coating of the GS-NSs with SiO2 shells having controlled thicknesses. Extinction spectra of the as-prepared nanoparticles indicated that the silica shell has a minimal effect on the LSPR peak of the gold-silver nanoshells.

We report the first in vitro enzymatic synthesis of paramagnetic and antiferromagnetic nanoparticles toward magnetic ELISA reporting. With our procedure, alkaline phosphatase catalyzes the dephosphorylation of l-ascorbic-2-phosphate, which then serves as a reducing agent for salts of iron, gadolinium, and holmium, forming magnetic precipitates of Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5. The nanoparticles were found to be paramagnetic at 300 K and antiferromagnetic under 25 K. Although weakly magnetic at 300 K, the room-temperature magnetization of the nanoparticles found here is considerably greater than that of analogous chemically-synthesized LnxFeyOz (Ln = Gd, Ho) samples reported previously. At 5 K, the nanoparticles showed a significantly higher saturation magnetization of 45 and 30 emu/g for Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5, respectively. Our approach of enzymatically synthesizing magnetic labels reduces the cost and avoids diffusional mass-transfer limitations associated with pre-synthesized magnetic reporter particles, while retaining the advantages of magnetic sensing.

The solution-phase self-assembly of bidentate 16-[3,5-bis(mercapto-methyl)phenoxy]hexadecanoic acid (BMPHA) on Au(111) was studied using nano-fabrication protocols with scanning probe nanolithography and immersion particle lithography. Molecularly thin films of BMPHA prepared by surface self-assembly have potential application as spatially selective layers in sensor designs. Either monolayer or bilayer films of BMPHA can be formed under ambient conditions, depending on the parameters of concentration and immersion intervals. Experiments with scanning probe-based lithography (nanoshaving and nanografting) were applied to measure the thickness of BMPHA films. The thickness of a monolayer and bilayer film of BMPHA on Au(111) were measured in situ with atomic force microscopy using n-octadecanethiol as an internal reference. Scanning probe-based nanofabrication provides a way to insert nanopatterns of a reference molecule of known dimensions within a matrix film of unknown thickness to enable a direct comparison of heights and surface morphology. Immersion particle lithography was used to prepare a periodic arrangement of nanoholes within films of BMPHA. The nanoholes could be backfilled by immersion in a SAM solution to produce nanodots of n-octadecanethiol surrounded by a film of BMPHA. Test platforms prepared by immersion particle lithography enables control of the dimensions of surface sites to construct supramolecular assemblies.

The solution self-assembly of multidentate organothiols onto Au(111) was studied in situ using scanning probe nanolithography and time-lapse atomic force microscopy (AFM). Self-assembled monolayers (SAMs) prepared from dilute solutions of multidentate thiols were found to assemble slowly, requiring more than six hours to generate films. A clean gold substrate was first imaged in ethanolic media using liquid AFM. Next, a 0.01 mM solution of multidentate thiol was injected into the liquid cell. As time progressed, molecular-level details of the surface changes at different time intervals were captured by successive AFM images. Scanning probe based nanofabrication was accomplished using protocols of nanografting and nanoshaving with n-alkanethiols and a tridentate molecule, 1,1,1-tris(mercaptomethyl)heptadecane (TMMH). Nanografted patterns of TMMH could be inscribed within n-alkanethiol SAMs; however, the molecular packing of the nanopatterns was less homogeneous compared to nanopatterns produced with monothiolates. The multidentate molecules have a more complex assembly pathway than monothiol counterparts, mediated by sequential steps of forming S–Au bonds to the substrate.

A “smart” core@shell composite nanoparticle (NP) having dual-response mechanisms (i.e., temperature and light) was synthesized, and its efficacy in the loading and release of small molecules was explored. These core@shell NPs are composed of an optically active gold nanoshell (GNS) core and a mesoporous (m-) silica layer (m-SiO2). The GNS@m-SiO2 nanoparticles are further encapsulated within a thermo-responsive poly(N-isopropylacrylamide-co-acrylic acid) hydrogel (PNIPAM-co-AA). The multi-responsive composite NPs were designed to create thermally and optically modulated drug-delivery vehicles with a m-SiO2 layer providing additional non-collapsible space for drug storage. The influence of the m-SiO2 layer on the efficacy of loading and release of methylene blue, which serves as a model for a small-molecule therapeutic drug, was evaluated. The “smart” core@shell composite NPs having a m-SiO2 layer demonstrated an improved capacity to load and release small molecules compared to the corresponding NPs with no m-SiO2 shell. Additionally, an efficient response by the composite NPs was successfully induced by the thermal energy generated from the gold nanoshell core upon exposure to near infrared (NIR) stimulation.

A custom-designed series of unsymmetrical spiroalkanedithiols having tailgroups comprised of a terminally fluorinated chain and a hydrocarbon chain of varying lengths were synthesized and used to prepare self-assembled monolayers (SAMs) on gold substrates. The specific structure of the adsorbates was of the form [CH3(CH2)n][CF3(CF2)7(CH2)8]C[CH2SH]2, where n = 7, 9, and 15 (designated as F8H10-C10, F8H10-C12, and F8H10-C18, respectively). The influence of the length of the hydrocarbon chain in the bidentate dithiol on the structure and interfacial properties of the monolayer was explored. A structurally analogous partially fluorinated monodentate alkanethiol and the corresponding normal alkanethiols were used to generate appropriate SAMs as reference systems. Measurements of ellipsometric thickness showed an unexpectedly low film thickness for the SAMs derived from the bidentate adsorbates, possibly due to disruptions in interchain packing caused by the fluorocarbon chains (i.e., phase-incompatible fluorocarbon-hydrocarbon interactions), ultimately giving rise to loosely packed and disordered films. Analysis by X-ray photoelectron spectroscopy (XPS) were also consistent with a model in which the films were loosely packed; additionally, the XPS spectra confirmed the attachment of the sulfur headgroups of the bidentate adsorbates onto the gold substrates. Studies of the SAMs by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) suggested that as the length of the hydrocarbon chain in the adsorbates was extended, a more ordered surface was achieved by reducing the tilt of the fluorocarbon segment. The wettability data indicated that the adsorbates with longer alkyl chains were less wettable than those with shorter alkyl chains, likely due to an increase in interchain van der Waals forces in the former.

The tremendous interest in magnetic nanoparticles (MNPs) is reflected in published research that ranges from novel methods of synthesis of unique nanoparticle shapes and composite structures to a large number of MNP characterization techniques, and finally to their use in many biomedical and nanotechnology-based applications. The knowledge gained from this vast body of research can be made more useful if we organize the associated results to correlate key magnetic properties with the parameters that influence them. Tuning these properties of MNPs will allow us to tailor nanoparticles for specific applications, thus increasing their effectiveness. The complex magnetic behavior exhibited by MNPs is governed by many factors; these factors can either improve or adversely affect the desired magnetic properties. In this report, we have outlined a matrix of parameters that can be varied to tune the magnetic properties of nanoparticles. For practical utility, this review focuses on the effect of size, shape, composition, and shell-core structure on saturation magnetization, coercivity, blocking temperature, and relaxation time.

Metal nanoparticles are extensively studied due to their unique chemical and physical properties, which differ from the properties of their respective bulk materials. Likewise, the properties of heterogeneous bimetallic structures are far more attractive than those of single-component nanoparticles. For example, the incorporation of a second metal into a nanoparticle structure influences and can potentially enhance the optical/plasmonic and magnetic properties of the material. This review focuses on the enhanced optical/plasmonic and magnetic properties offered by bimetallic nanoparticles and their corresponding impact on biological applications. In this review, we summarize the predominant structures of bimetallic nanoparticles, outline their synthesis methods, and highlight their use in biological applications, both diagnostic and therapeutic, which are dictated by their various optical/plasmonic and magnetic properties.

Gold nanoshells (~160 nm in diameter) were encapsulated within a shell of temperature-responsive poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) using a surface-bound rationally-designed free radical initiator in water for the development of a photothermally-induced drug-delivery system. The morphologies of the resultant hydrogel-coated nanoshells were analyzed by scanning electron microscopy (SEM), while the temperature-responsive behavior of the nanoparticles was characterized by dynamic light scattering (DLS). The diameter of the P(NIPAM-co-AA) encapsulated nanoshells decreased as the solution temperature was increased, indicating a collapse of the hydrogel layer with increasing temperatures. In addition, the optical properties of the composite nanoshells were studied by UV-visible spectroscopy. The surface plasmon resonance (SPR) peak of the hydrogel-coated nanoshells appeared at ~800 nm, which lies within the tissue-transparent range that is important for biomedical applications. Furthermore, the periphery of the particles was conjugated with the model protein avidin to modify the hydrogel-coated nanoshells with a fluorescent-tagged biotin, biotin-4-fluorescein (biotin-4-FITC), for colorimetric imaging/monitoring.

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.