ToF-SIMS analysis of ultrathin films and their fragmentation patterns.

Organic thin films are of great interest due to their intriguing interfacial and functional properties, especially for device applications such as thin-film transistors and sensors. As their thickness approaches single nanometer thickness, characterization and interpretation of the extracted data become increasingly complex. In this study, plasma polymerization is used to construct ultrathin films that range in thickness from 1 to 20 nm, and time-of-flight secondary ion mass spectrometry coupled with principal component analysis is used to investigate the effects of film thickness on the resulting spectra.

Quantitative evaluation of perfluorinated alkanethiol molecular order on gold surfaces.

Self-assembled monolayers (SAMs) of perfluoroalkanethiols [CF3(CF2)xCH2CH2SH (x = 3, 5, 7, and 9)] on gold were characterized by x-ray photoelectron spectroscopy (XPS), near edge x-ray absorption fine structure (NEXAFS), and static time-of-flight secondary ion mass spectrometry (ToF-SIMS). Perfluoroalkanethiols of several chain lengths were synthesized using a known hydride reduction method for transforming commercially available perfluoroalkyliodides to corresponding perfluoroalkanethiols. This strategy provides improved product yields compared to other known routes based on hydrolysis from the common thioacetyl perfluoroalkyl intermediate.

Developments and Ongoing Challenges for Analysis of Surface-Bound Proteins.

Proteins at surfaces and interfaces play important roles in the function and performance of materials in applications ranging from diagnostic assays to biomedical devices. To improve the performance of these materials, detailed molecular structure (conformation and orientation) along with the identity and concentrations of the surface-bound proteins on those materials must be determined. This article describes radiolabeling, surface plasmon resonance, quartz crystal microbalance with dissipation, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, sum frequency generation spectroscopy, and computational techniques along with the information each technique provides for characterizing protein films.

Utilization of chromogenic enzyme substrates for signal amplification in multiplexed detection of biomolecules using surface mass spectrometry.

MicroRNAs (miRNAs) are important post-transcriptional gene regulators and can serve as potential biomarkers for many diseases. Most of the current miRNA detection techniques require purification from biological samples, amplification, labeling, or tagging, which makes quantitative analysis of clinically relevant samples challenging. Here we present a new strategy for the detection of miRNAs with uniformity over a large area based on signal amplification using enzymatic reactions and measurements using time-of-flight secondary ion mass spectrometry (ToF-SIMS), a sensitive surface analysis tool.

Evaluation of surface layer stability of surface-modified polyester biomaterials.

Surface modification of biomaterials is a strategy used to improve cellular and in vivo outcomes. However, most studies do not evaluate the lifetime of the introduced surface layer, which is an important aspect affecting how a biomaterial will interact with a cellular environment both in the short and in the long term. This study evaluated the surface layer stability in vitro in buffer solution of materials produced from poly(lactic-co-glycolic acid) (50:50) and polycaprolactone modified by hydrolysis and/or grafting of hydrophilic polymers using grafting from approaches.

Long-term hydrolytic degradation study of polycaprolactone films and fibers grafted with poly(sodium styrene sulfonate): Mechanism study and cell response.

Polycaprolactone (PCL) is a widely used biodegradable polyester for tissue engineering applications when long-term degradation is preferred. In this article, we focused on the analysis of the hydrolytic degradation of virgin and bioactive poly(sodium styrene sulfonate) (pNaSS) functionalized PCL surfaces under simulated physiological conditions (phosphate buffer saline at 25 and 37 °C) for up to 120 weeks with the aim of applying bioactive PCL for ligament tissue engineering. Techniques used to characterize the bulk and surface degradation indicated that PCL was hydrolyzed by a bulk degradation mode with an accelerated degradation-three times increased rate constant-for pNaSS grafted PCL at 37 °C when compared to virgin PCL at 25 °C.

Polymer Surface Analysis: The Leadership and Contributions of David Briggs.

David Briggs was a surface analysis pioneer. Starting in 1970 and continuing throughout his career, Dave used his expertise, vision and ability to quickly master new surface analysis methods and solve important industrial problems. It certainly helped that he was an outstanding fund raiser in both industrial and academic settings, which ensured he always had an impressive array of the latest, most advanced surface analysis instrumentation at his disposal.

Surface analysis tools for characterizing biological materials.

Surfaces represent a unique state of matter that typically have significantly different compositions and structures from the bulk of a material. Since surfaces are the interface between a material and its environment, they play an important role in how a material interacts with its environment. Thus, it is essential to characterize, in as much detail as possible, the surface structure and composition of a material.

Characterizing protein G B1 orientation and its effect on immunoglobulin G antibody binding using XPS, ToF-SIMS, and quartz crystal microbalance with dissipation monitoring.

Controlling how proteins are immobilized (e.g., controlling their orientation and conformation) is essential for developing and optimizing the performance of in vitro protein-binding devices, such as enzyme-linked immunosorbent assays.

A Versatile Catalyst-Free Perfluoroaryl Azide-Aldehyde-Amine Conjugation Reaction.

A tri-component reaction, involving an electrophilically-activated perfluoroaryl azide, an enolizable aldehyde and an amine, reacts readily at room temperature without any catalysts in solvents including aqueous conditions to yield a stable amidine conjugate. The versatility of this reaction is demonstrated in the conjugation of an amino acid without prior protection of the carboxyl group, and in the synthesize antibiotic-nanoparticle conjugates.

Analysis of early cellular responses of anterior cruciate ligament fibroblasts seeded on different molecular weight polycaprolactone films functionalized by a bioactive poly(sodium styrene sulfonate) polymer.

With the growing number of anterior cruciate ligament (ACL) ruptures and the increased interest for regenerative medicine procedures, many studies are now concentrated on developing bioactive and biodegradable synthetic ligaments. For this application, the choice of raw materials with appropriate physicochemical characteristics and long-term degradation features is essential. Polycaprolactone (PCL) has the advantage of slow degradation that depends on its molecular weight.

Vibrational Sum-Frequency Scattering as a Sensitive Approach to Detect Structural Changes in Collagen Fibers Treated with Surfactants.

Optimizing protocols so that the structure of the collagen fibers in the extracellular matrix remains intact during the decellularization process requires techniques with high structural sensitivity, especially for the surface region of the collagen fibers. Here, we demonstrate that vibrational sum-frequency scattering (SFS) spectroscopy in the protein-specific amide I region provides vibrational spectra and scattering patterns characteristic of protein fiber networks self-assembled in vitro from collagen type I, which are kept in aqueous environments during the analysis. At scattering angles away from the phase-matched direction, the relative strengths of various polarization combinations are highly reproducible, and changes in their ratios can be followed in real time during exposure to sodium dodecyl sulfate surfactant solutions.

Structure of von Willebrand factor A1 on polystyrene determined from experimental and calculated sum frequency generation spectra.

The blood-clotting protein von Willebrand factor (vWF) can be activated by small molecules, high shear stress, and interactions with interfaces. It subsequently binds platelet receptor glycoprotein Ibα (GPIbα) at the surface of platelets, thereby playing a crucial role in blood clotting due to platelet activation, which is an important process to consider in the design of cardiovascular implants and biomaterials used in blood-contacting applications. The influence of surfaces on the activation and the molecular-level structure of surface-bound vWF is largely unknown.

Surface Analysis: From Single Crystals to Biomaterials.

Surfaces and interfaces play a critical role in material performance in many applications including catalysis, biomaterials, microelectronics, tribology and adhesion. Characterizing the important surfaces and interfaces involved in each application may present different challenges, but the approach to investigating them often is rather similar. Specialized instrumentation is typically used to probe the surface region of a material and often times it is required to develop new instrumentation and data analysis methods to obtain the desired information.

Stabilization of dry protein coatings with compatible solutes.

Exposure of protein modified surfaces to air may be necessary in several applications. For example, air contact may be inevitable during the implantation of biomedical devices, for analysis of protein modified surfaces, or for sensor applications. Protein coatings are very sensitive to dehydration and can undergo significant and irreversible alterations of their conformations upon exposure to air.

Nonlinear Optical Methods for Characterization of Molecular Structure and Surface Chemistry.

The principles, strengths and limitations of several nonlinear optical (NLO) methods for characterizing biological systems are reviewed. NLO methods encompass a wide range of approaches that can be used for real-time, in-situ characterization of biological systems, typically in a label-free mode. Multiphoton excitation fluorescence (MPEF) is widely used for high-quality imaging based on electronic transitions, but lacks interface specificity.

Grafting of Bioactive Polymers with Various Architectures: A Versatile Tool for Preparing Antibacterial Infection and Biocompatible Surfaces.

The aim of this Research Article is to present three different techniques of poly(sodium styrene sulfonate) (polyNaSS) covalent grafting onto titanium (Ti) surfaces and study the influence of their architecture on biological response. Two of them are "grafting from" techniques requiring an activation step either by thermal or UV irradiation. The third method is a "grafting to" technique involving an anchorage molecule onto which polyNaSS synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization is clicked.

Grafting of architecture controlled poly(styrene sodium sulfonate) onto titanium surfaces using bio-adhesive molecules: Surface characterization and biological properties.

This contribution reports on grafting of bioactive polymers such as poly(sodium styrene sulfonate) (polyNaSS) onto titanium (Ti) surfaces. This grafting process uses a modified dopamine as an anchor molecule to link polyNaSS to the Ti surface. The grafting process combines reversible addition-fragmentation chain transfer polymerization, postpolymerization modification, and thiol-ene chemistry.

Orientation and conformation of osteocalcin adsorbed onto calcium phosphate and silica surfaces.

Adsorption isotherms, circular dichroism (CD) spectroscopy, x-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to investigate the adsorption of human osteocalcin (hOC) and decarboxylated (i.e., Gla converted back to Glu) hOC (dhOC) onto various calcium phosphate surfaces as well as silica surfaces.

Biomedical surface analysis: Evolution and future directions (Review).

This review describes some of the major advances made in biomedical surface analysis over the past 30-40 years. Starting from a single technique analysis of homogeneous surfaces, it has been developed into a complementary, multitechnique approach for obtaining detailed, comprehensive information about a wide range of surfaces and interfaces of interest to the biomedical community. Significant advances have been made in each surface analysis technique, as well as how the techniques are combined to provide detailed information about biological surfaces and interfaces.

Predicting the orientation of protein G B1 on hydrophobic surfaces using Monte Carlo simulations.

A Monte Carlo algorithm was developed to predict the most likely orientations of protein G B1, an immunoglobulin G (IgG) antibody-binding domain of protein G, adsorbed onto a hydrophobic surface. At each Monte Carlo step, the protein was rotated and translated as a rigid body. The assumption about rigidity was supported by quartz crystal microbalance with dissipation monitoring experiments, which indicated that protein G B1 adsorbed on a polystyrene surface with its native structure conserved and showed that its IgG antibody-binding activity was retained.

Multitechnique characterization of oligo(ethylene glycol) functionalized gold nanoparticles.

Gold nanoparticles (AuNPs) with average diameters of ∼14 and ∼40 nm, as well as flat gold coated silicon wafers, were functionalized with oligo ethylene glycol (OEG) terminated 1-undecanethiol (HS-CH) self-assembled monolayers (SAMs). Both hydroxyl [(OEG)OH] and methoxy [(OEG)OMe] terminated SAMs were prepared. The AuNPs were characterized with transmission electron microscopy (TEM), time of flight secondary ion mass spectrometry (ToF-SIMS), x-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier infrared spectroscopy (ATR-FTIR), and low-energy ion scattering (LEIS).