Terminal Thiol Groups Research Articles

Poly(ethylene glycol) analogs grafted with low molecular weight poly(ethylene imine) as non-viral gene vectors

A novel class of non-viral gene vectors consisting of low molecular weight poly(ethylene imine) (PEI) (molecular weight 800 Da) grafted onto degradable linear poly(ethylene glycol) (PEG) analogs was synthesized. First, a Michael addition reaction between poly(ethylene glycol) diacrylates (PEGDA) (molecular weight 258 Da) and d, l-dithiothreitol (DTT) was carried out to generate a linear polymer (PEG–DTT) having a terminal thiol, methacrylate and pendant hydroxyl functional groups. Five PEG–DTT analogs were synthesized by varying the molar ratio of diacrylates to thiols from 1.2:1 to 1:1.2. Then PEI (800 Da) was grafted onto the main chain of the PEG–DTTs using 1,1′-carbonyldiimidazole as the linker. The above reaction gave rise to a new class of non-viral gene vectors, (PEG–DTT)–g-PEI copolymers, which can effectively complex DNA to form nanoparticles. The molecular weights and structures of the copolymers were characterized by gel permeation chromatography, 1H nuclear magnetic resonance and Fourier transform infrared spectroscopy. The size of the nanoparticles was <200 nm and the surface charge of the nanoparticles, expressed as the zeta potential, was between +20 and +40 mV. Cytotoxicity assays showed that the copolymers exhibited much lower cytotoxicities than high molecular weight PEI (25 kDa). Transfection was performed in cultured HeLa, HepG2, MCF-7 and COS-7 cells. The copolymers showed higher transfection efficiencies than PEI (25 kDa) tested in four cell lines. The presence of serum (up to 30%) had no inhibitory effect on the transfection efficiency. These results indicate that this new class of non-viral gene vectors may be a promising gene carrier that is worth further investigation.

Self-Assembly of Gold Nanoparticles and Polystyrene: A Highly Versatile Approach to the Preparation of Colloidal Particles with Polystyrene Cores and Gold Nanoparticle Coronae

Colloidal particles with polystyrene (PS) cores and gold nanoparticle (AuNP) coronae were prepared on the basis of the self-assembly of AuNP's and PS. Citrate-stabilized AuNP's were dispersed in aqueous solution, and PS with thiol terminal groups (PS-SH) was dissolved in toluene. A stable emulsion was obtained by mixing the two solutions. Optical microscope images indicate that after grafting of PS-SH to the citrate-stabilized AuNP's at liquid-liquid interface, the interfacial tension is reduced and the average size of toluene droplets in the emulsion decreases. Transmission electron microscope (TEM) results also prove the grafting of PS-SH to AuNP's and the location of the hybrid nanoparticles at the liquid-liquid interface. Colloidal particles with PS cores and AuNP coronae were prepared by adding the emulsion to excess methanol. The weight ratio of PS-SH to AuNP exerts a significant effect on the size of colloidal particles. TEM and dynamic light scattering results both indicate that the size of colloidal particles increases with the weight ratio. The application of the core-shell-structured colloidal particles to protein separation was also investigated in this research. Colloidal particles with PS-coated magnetic nanoparticles in the cores were also prepared by this strategy.

Direct colorimetric diagnosis of pathogen infections by utilizing thiol-labeled PCR primers and unmodified gold nanoparticles

We describe here a greatly simplified colorimetric detection method to identify PCR-amplified nucleic acids. Our method relies on the PCR product having thiol group at one end, which is generated by employing thiolated PCR primer. After PCR amplification reaction, unmodified gold nanoparticles (AuNPs) are added into the reaction tube followed by the addition of NaCl to induce the aggregation of AuNPs. The PCR products strongly bind to the surface of AuNPs through the interaction of the terminal thiol groups and the long chain of DNA which has abundant negative charges enhances the electrostatic and steric repulsion among AuNPs, which consequently leads to the prevention of the salt-induced aggregation. As a result, the color of AuNPs remains red in the presence of the PCR-amplified nucleic acids, while the AuNPs change its color from red to blue due to the salt-induced aggregation in the absence of the PCR products. This simple but very efficient colorimetric strategy was successfully demonstrated by diagnosing Chlamydia infection using a real human urine sample. Since the results can be clearly seen with the naked eye without any complicated step such as surface modification of AuNPs or PCR product purification, this method can be easily applied to point-of-care diagnosis.

Composites of Poly(Keto-Sulfide)–Epoxy Resin Systems and Their Thermal and Mechanical Properties

A novel matrix resin system, poly(keto-sulfide)–epoxy resin, has been developed. The poly(keto-sulfide)s (PKS), based on various ketones, formaldehyde, and sodium hydrogen sulfide (NaSH), were prepared by the reported process. These (PKS) having terminal thiol (–SH) groups were used for curing commercial epoxy resin (i.e., diglycidyl ether of bisphenol A – DGEBA), to fabricate crosslinked epoxy-poly(keto-sulfide) resin glass fiber-reinforced composites (GRC). Various epoxy/hardener (PKS) mixing ratios were used, and the curing of epoxy-PKS has been monitored using differential scanning calorimetry (DSC) in dynamic mode. Based on DSC parameters the GRC of epoxy-PKS were prepared and characterized by thermal and mechanical methods. The variation in resin/hardener ratio led to variations in thermal and mechanical properties.

New development of ‘sono-functional’ molecule: Binding to DNA by sonication

‘Sono-functional’ molecule 1 was prepared and its binding properties to DNA under ultrasonic irradiation were studied by UV spectra. As a result, it was shown that the binding of 1 to DNA was enhanced by ultrasound. Being compared with its precursor 2, it is clear that terminal thiol groups of 1 play an important role in specific binding to DNA.

Ab initio study of noncovalent sidewall functionalization of carbon nanotubes

We investigated noncovalent molecular adsorptions onto carbon nanotubes (CNTs), using density-functional theory methods including recently developed hybrid functionals. Planar aromatic molecules have greater binding strength than fully saturated nonaromatic molecules, and adsorption geometries are consistent with the features of intermolecular π−π stacking. We show that modifications with alcohol or a thiol terminal group increase the adsorption strength consistently throughout the considered molecules. This result may be used in experiments involving noncovalent sidewall functionalizations of CNTs.

A Versatile Approach to the Fabrication of Palladium Hollow Spheres with Aluminiumoxide Nanoparticles as Template

Palladium hollow nanospheres were prepared by the adsorption of metal nanoparticles onto functionalized gamma-Al2O3 templates. The silanizing agent 3-mercaptopropyl trimethoxysilane was reacted with the surface of the gamma-Al2O3 templates to afford thiol-terminal groups. Metal layers of palladium were coated directly on the gamma-Al2O3 templates by increasing the temperature stepwise. Then, the dissolution of the gamma-Al2O3 template using 40 wt% HF solution enabled the formation of self-organized metallic palladium hollow nanospheres. The palladium hollow nanospheres were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) techniques.

Construction of Oligonucleotide Microarrays (Biochips) via Thioether Linkage for the Detection of Bacterial Meningitis

Oligonucleotide-based arrays are increasingly becoming useful tools for the analysis of gene expression and single-nucleotide polymorphism. Here, we report a method that allows the direct immobilization of thiolated oligonucleotides onto an epoxy-activated glass surface via a stable thioether linkage under microwaves. The described chemistry efficiently immobilizes the probes via terminal thiol groups with uniform spot morphology. The thioether linkage could endure repeated PCR-like heat cycling with only 2.5% loss after 20 cycles, indicating that the chemistry can be used in integrated PCR/microarray devices. The highlighting feature of the proposed method is that the detection limit for the probe concentration can be reduced to 0.25 microM with 20-mer oligonucleotides. The efficiency of the projected method (approximately 33%) indicates its advantage over the existing standard methods, viz., NTMTA (approximately 9.8%), epoxide-amine (approximately 9.8%) and disulfide (approximately 1.7%). The constructed microarrays were validated through the detection of base mismatches and bacterial meningitis. These features make the projected strategy ideal for manufacturing oligonucleotide arrays and detection of mismatches and bacterial diseases.

Fabrication of a surface plasmon resonance biosensor based on gold nanoparticles chemisorbed onto a 1,10-decanedithiol self-assembled monolayer

We have investigated the fabrication of surface plasmon resonance (SPR) biosensors using self-assembled monolayers (SAMs) and adsorbed gold nanoparticles. The SAM of 1,10-decanedithiol was first fabricated onto a gold substrate. Gold nanoparticles were then chemisorbed onto the SAM surface by bonding with the terminal thiol groups, forming a sensor that can be used to immobilize proteins. Bovine serum albumin (BSA) was used as a test protein in this study. Several spectroscopic and microscopic techniques were used to investigate both the SAM and the chemisorption of gold nanoparticles at the SAM surface. Our results confirm the covalent bonding of the gold nanoparticles onto the SAM. Surface plasmon resonance (SPR) was used to study both the adsorption of BSA to the SAM surface and to the gold nanoparticle-coated SAM. For SAM surfaces with adsorbed gold nanoparticles a larger SPR response to BSA than to the sensors with a bare SAM is observed.

Engineering the Spatial Selectivity of Surfaces at the Nanoscale Using Particle Lithography Combined with Vapor Deposition of Organosilanes

Particle lithography is a practical approach to generate millions of organosilane nanostructures on various surfaces, without the need for vacuum environments or expensive instrumentation. This report describes a stepwise chemistry route to prepare organosilane nanostructures and then apply the patterns as a spatially selective foundation to attach gold nanoparticles. Sites with thiol terminal groups were sufficiently small to localize the attachment of clusters of 2-5 nanoparticles. Basic steps such as centrifuging, drying, heating, and rinsing were used to generate arrays of regular nanopatterns. Close-packed films of monodisperse latex spheres can be used as an evaporative mask to spatially direct the placement of nanoscopic amounts of water on surfaces. Vapor phase organosilanes deposit selectively at areas of the surface containing water residues to generate nanostructures with regular thickness, geometry, and periodicity as revealed in atomic force microscopy images. The area of contact underneath the mesospheres is effectively masked for later synthetic steps, providing exquisite control of surface coverage and local chemistry. By judicious selection in designing the terminal groups of organosilanes, surface sites can be engineered at the nanoscale for building more complex structures. The density of the nanopatterns and surface coverage scale predictably with the diameter of the mesoparticle masks. The examples presented definitively illustrate the capabilities of using the chemistry of molecularly thin films of organosilanes to spatially define the selectivity of surfaces at very small size scales.

Characterization and tribological investigation of self-assembled MPTS-MPTES/RE composite films

γ-mercapto-propyl trimethoxysilane (MPTS) and γ-methacryloxy propyltrimethoxysilane (MPTES) were self-assembled on a hydroxylated glass substrate to form a two-dimensional organic monolayer (MPTS-MPTES SAM). The terminal thiol groups (–SH) in the MPTS-MPTES SAM were in-situ oxidized into sulfonic acid groups (–SO 3H) to endow the film with good chemisorption ability. Then rare earth (RE) (lanthanum-based) composite thin films were prepared by self-assembly technique based on the as-prepared SAM, taking advantage of the chemisorption ability of the sulfonic acid groups. Automatic force microscope (AFM), X-ray photoelectron spectrometry (XPS), contact angle measurement and ellipsometer were used to characterize MPTS-MPTES/RE composite films. The macrofriction and wear behaviors of the films sliding against an AISI-52100 steel ball were examined on a unidirectional friction and wear tester, and the worn surface morphologies were observed on an AFM. The results showed that MPTS-MPTES/RE films had a low friction coefficient (0.09) and a long wear life (5980 sliding pass) at a light load (50 mN). It indicated that the superior tribological properties of the MPTS-MPTES/RE composite films were attributed to the special characteristic of RE elements, the mobility of the films and good bonding strength.

Bromine-containing functional nanolayers for biomolecule immobilization

Bromine-containing nanolayers are deposited by pulsed plasma deposition of 2-bromoethylacrylate. Subsequent covalent immobilization of single-strand DNA onto these films is achieved via the reaction with a terminal thiol group linker contained in the oligonucleotide.

Selective Protein Patterning Based on the Micro-Structured Organosilane Self-Assembled Monolayer by Vacuum Ultraviolet Light Lithography

We have succeeded to immobilize fluorescent proteins selectively using a micro-structured organosilane self-assembled monolayer as a template. An organosilane layer with amino terminal group was formed on a thermally oxidized Si wafer by liquid-phase method and then was pattern-etched by vacuum ultraviolet light (VUV). The second organosilane layer with thiol terminal group was deposited on the etched area by chemical vapor surface modification method (CVSM). These micro-structured organosilane layer containing two reactive terminal groups were chemically modified using bi-functional linkers. Two kinds of fluorescent protein, Enhanced Cyan Fluorescent Protein (ECFP) and R-phycoerythrin were selectively immobilized on the chemically modified surface.

Thiacalix[4] arenes with terminal thiol groups at the lower rim: synthesis and structure

Methods were developed for the synthesis of ω-mercaptoalkoxy derivatives of thiacalix[4]-arenes in the 1,3-alternate conformation containing different numbers (2–5) of methylene spacers at the lower rim. The hydrazinolysis of the corresponding thioacetates is the most efficient method for the synthesis of these compounds.

An Iron(II) Spin‐Transition Compound with Thiol Anchoring Groups

AbstractThe synthesis and characterisation of the complex [FeII(L)2](ClO4)2 [L = S‐(4‐{[2,6‐(Dipyrazol‐1‐yl)pyrid‐4‐yl]ethynyl}phenyl) ethanethioate] carrying both a spin‐transition core and acetyl‐protected terminal thiol groups is described. The compound exhibits a reversible, thermally driven solid‐state spin transition at 277 K with a hysteresis loop of ca. 8 K. The unique combination of the bistable spin‐transition property with thiol anchoring groups sets the basis for the investigation of the spin‐transition switching phenomenon at a single‐molecule level. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)

Temporal Evolution of the Composition of Mixed Monolayers on TiO2 Surfaces: Evidence for a Dimerization-Induced Chelate Effect

Mixed monolayers of octanoic acid (OA) and 16-mercaptohexadecanoic acid (MHDA) were adsorbed to nanocrystalline TiO(2) films from mixed solutions in tetrahydrofuran. For a range of solution compositions, the mole fraction of MHDA within the mixed monolayers (chi (MHDA,surf)) exceeded that of the coadsorption solution. In addition, chi (MHDA,surf) increased with time, while the sum of the surface coverages of MHDA and OA remained constant. To account for these effects, we propose a mechanism involving disulfide formation between the terminal thiol groups of surface-adsorbed MHDA molecules. Disulfide formation leads to an increase in the surface adduct formation constant ( K(ad)) of dimeric MHDA, causing the gradual displacement of OA from the surface. The mechanism is supported by spectroscopic evidence and desorption kinetics. These are the first examples of mixed monolayers that undergo time-dependent compositional changes as a result of covalent bond formation between surfactants. Our findings illustrate that dimerization and other intermolecular interactions between surfactants may dramatically influence the composition and terminal functionalization of a wide range of mixed monolayer systems.

Chiral Elaboration of Gold Nanoparticle Surfaces by Bis(binaphthyl) Groups

The synthesis of a family of bis(binaphthyl)-based compounds for the chiral modification of gold nanoparticle surfaces is described. In these systems, two (S)-1,1′-bi-2-naphthol groups are linked to one another by a single diethanolamine-derived bridge, the nitrogen atom of which serves as an anchor for the attachment of an alkanethiol tether of 6, 10, or 12 methylene units in length. The terminal thiol group allows the production of surface-elaborated gold nanoparticles of 2.1 ± 0.6 nm diameter by a ‘direct synthesis’ method.

Preparation of poly(styrene‐b‐N‐isopropylacrylamide) micelles surface‐linked with gold nanoparticles and thermo‐responsive ultraviolet–visible absorbance

AbstractPoly(styrene‐b‐N‐isopropylacrylamide) (PSt‐b‐PNIPAM) with dithiobenzoate terminal group was synthesized by reversible addition‐fragmentation‐transfer polymerization. The dithiobenzoate terminal group was converted into thiol terminal group with NaBH4, resulting thiol‐terminated PSt‐b‐PNIPAM‐SH. After PSt‐b‐PNIPAM‐SH assembled into core‐shell micelles in aqueous solution, gold nanoparticles were in situ surface‐linked onto the micelles through the reduction of gold precursor anions with NaBH4. Thus, temperature responsive core/shell micelles of PSt‐b‐PNIPAM surface‐linked with gold nanoparticles (PSt‐b‐PNIPAM‐Au micelles) were obtained. Transmission Electron Microscopy revealed the successful linkage of gold nanoparticles and the dependence of the number of gold nanoparticles per micelle on the molar ratio of HAuCl4 to thiol group of PSt‐b‐PNIPAM. Dynamic Light Scattering analysis demonstrated thermo‐responsive behavior of PSt‐b‐PNIPAM‐Au micelles. Changing the temperature of PSt‐b‐PNIPAM‐Au micelles led to the shrinkage of PNIPAM shell and allowed to tune the distance between gold nanoparticles. Ultraviolet–visible (UV–vis) spectroscopy clearly showed the reversible modulation of UV–vis absorbance of PSt‐b‐PNIPAM‐Au micelles upon heating and cooling. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5156–5163, 2007

Adsorption of CdSe Nanoparticles to Thiolated TiO2 Surfaces: Influence of Intralayer Disulfide Formation on CdSe Surface Coverage

Mixed monolayers of hexadecanoic acid (HDA) and 16-mercaptohexadecanoic acid (MHDA) were adsorbed to nanocrystalline TiO2 films, and CdSe nanoparticles were attached to the mixed monolayer functionalized surfaces. IR absorption spectroscopy was used to characterize the equilibrium binding of HDA and MHDA to TiO2. Surface adduct formation constants (Kad) of (4+/-2)x10(3) M(-1) and (6+/-4)x10(3) M(-1) were measured for HDA and MHDA, respectively. CdSe nanoparticles were adsorbed to the terminal thiol groups of MHDA. The surface coverage of CdSe was greater on mixed monolayers, consisting of approximately 12% MHDA and 88% HDA, than on pure MHDA monolayers. A mechanism is proposed wherein intralayer disulfide formation between MHDA thiol groups causes decreased reactivity toward CdSe nanoparticles. Disulfide formation is less significant at low fractional surface coverages of MHDA. The mechanism is supported by an increase of CdSe adsorption upon chemical reduction of surface disulfides to thiols. Our findings highlight the effect of intermolecular interactions on the affinity of nanoparticles for monolayer-functionalized surfaces.

Poly(vinylpyrrolidone) for Bioconjugation and Surface Ligand Immobilization

Poly(vinylpyrrolidone) (PVP), a nonionic and nontoxic polymer with antifouling properties, has been synthesized via RAFT polymerization to obtain thiol-terminated PVP. We demonstrate that when the polymer is adsorbed onto the surface of colloidal silica particles, the terminal thiol groups of PVP remain accessible for chemical modification and lend themselves to the immobilization of ligands. We show that ligand attachment onto the surface via conjugation to PVP is reversible, as the polymer can be desorbed from the surface for conjugate and surface recovery. We present the conjugation of a model peptide and an oligonucleotide to PVP via the polymer terminal thiol and demonstrate that conjugates remain functional in molecular recognition assay. The developed technique offers a novel method to functionalize low-fouling surfaces for a variety of biomedical applications and presents opportunities to use PVP as a macromolecular drug carrier.