XPS and ToF-SIMS Characterization of New Biodegradable Poly(Peptide-Urethane-Urea) Block Copolymers.

New, linear, segmented poly(peptide-urethane-urea) (PPUU) block copolymers are synthesized and their surface compositions are characterized with angle dependent X-ray photoelectron spectroscopy (ADXPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). These new PPUU block copolymers contain three types of segments. The soft segment (SS) is poly(caprolactone diol) (PCL). The hard segment is lysine diisocyanate with a hydrazine chain extender. The oligopeptide segment (OPS) contains three types of amino acids (proline, hydroxyproline, and glycine). Incorporation of the OPS into the polyurethane backbone is done to provide a synthetic polymer material with controllable biodegradation properties. As biodegradation processes normally are initiated at the interface between the biomaterial and the living tissue, it is important to characterize the surface composition of biomaterials. ADXPS and ToF-SIMS results show that the surfaces of all four polymers are enriched with the PCL SS, the most hydrophobic component of the three polymer segments.

Versailles Project on Advanced Materials and Standards interlaboratory study on intensity calibration for x-ray photoelectron spectroscopy instruments using low-density polyethylene.

We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.

Direct Characterization of Polymer Encapsulated CdSe/CdS/ZnS Quantum Dots.

Surface engineering advances of semiconductor quantum dots (QDs) have enabled their application to molecular labeling, disease diagnostics and tumor imaging. For biological applications, hydrophobic core/shell QDs are transferred into aqueous solutions through the incorporation of water-solubility imparting moieties, typically achieved via direct exchange of the native surface passivating ligands or indirectly through the adsorption of polymers. Although polymeric encapsulation has gained wide acceptance, there are few reports addressing the characterization of the adsorbed polymers and existing theoretical analyses are typically based on simple geometric models. In this work, we experimentally characterize and quantify water-soluble QDs prepared by adsorption of amphiphilic poly(maleic anhydride-alt-1-tetradecene) (PMAT, MW~9000) onto commercially available CdSe/CdS/ZnS (CdSe/CdS/ZnS-PMAT). Using x-ray photoelectron spectroscopy (XPS) we determined that ~15 PMAT molecules are adsorbed onto each QD and sum frequency generation (SFG) vibrational spectra was utilized to investigate the mechanism of interaction between PMAT molecules and the QD surface. Importantly, when employed together, these techniques constitute a platform with which to investigate any polymer-nanoparticle complex in general.

Analysis of the surface density and reactivity of perfluorophenylazide and the impact on ligand immobilization.

Perfluorophenylazide (PFPA) chemistry is a novel method for tailoring the surface properties of solid surfaces and nanoparticles. It is general and versatile, and has proven to be an efficient way to immobilize graphene, proteins, carbohydrates, and synthetic polymers. The main thrust of this work is to provide a detailed investigation on the chemical composition and surface density of the PFPA tailored surface. Specifically, gold surfaces were treated with PFPA-derivatized (11-mercaptoundecyl)tetra(ethylene glycol) (PFPA-MUTEG) mixed with 2-[2-(2-mercaptoethoxy)ethoxy]ethanol (MDEG) at varying solution mole ratios. Complementary analytical techniques were employed to characterize the resulting films including Fourier transform infrared spectroscopy to detect fingerprints of the PFPA group, x-ray photoelectron spectroscopy and ellipsometry to study the homogeneity and uniformity of the films, and near edge x-ray absorption fine structures to study the electronic and chemical structure of the PFPA groups. Results from these studies show that the films prepared from 90:10 and 80:20 PFPA-MUTEG/MDEG mixed solutions exhibited the highest surface density of PFPA and the most homogeneous coverage on the surface. A functional assay using surface plasmon resonance with carbohydrates covalently immobilized onto the PFPA-modified surfaces showed the highest binding affinity for lectin on the PFPA-MUTEG/MDEG film prepared from a 90:10 solution.

Grafting titanium nitride surfaces with sodium styrene sulfonate thin films.

The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm(2).

X-Ray Photoelectron Spectroscopy Investigation of the Nitrogen Species in Photoactive Perfluorophenylazide-Modified Surfaces.

X-ray Photoelectron Spectroscopy (XPS) was used to characterize the nitrogen species in perfluorophenylazide (PFPA) self-assembled monolayers. PFPA chemistry is a novel immobilization method for tailoring the surface properties of materials. It is a simple route for the efficient immobilization of graphene, proteins, carbohydrates and synthetic polymers onto a variety of surfaces. Upon light irradiation, the azido group in PFPA is converted to a highly reactive singlet nitrene species that readily undergoes CH insertion and C=C addition reactions. Here, the challenge of characterizing the PFPA modified surfaces was addressed by detailed XPS experimental analyses. The three nitrogen peaks detected in the XPS N1s spectra were assigned to amine/amide (400.5 eV) and azide (402.1 and 405.6 eV) species. The observed 2:1 ratio of the areas from the 402.1 eV to 405.6 eV peaks suggests the assignment of the peak at 402.1 eV to the two outer nitrogen atoms in the azido group and assignment of the peak at 405.6 eV to the central nitrogen atom in the azido group. The azide decomposition as the function of x-ray exposure was also determined. Finally, XPS analyses were conducted on patterned graphene to investigate the covalent bond formation between the PFPA and graphene. This study provides strong evidence for the formation of covalent bonds during the PFPA photocoupling process.

Discovery of the surface polarity gradient on iridescent Morpho butterfly scales reveals a mechanism of their selective vapor response.

For almost a century, the iridescence of tropical Morpho butterfly scales has been known to originate from 3D vertical ridge structures of stacked periodic layers of cuticle separated by air gaps. Here we describe a biological pattern of surface functionality that we have found in these photonic structures. This pattern is a gradient of surface polarity of the ridge structures that runs from their polar tops to their less-polar bottoms. This finding shows a biological pattern design that could stimulate numerous technological applications ranging from photonic security tags to self-cleaning surfaces, gas separators, protective clothing, sensors, and many others. As an important first step, this biomaterial property and our knowledge of its basis has allowed us to unveil a general mechanism of selective vapor response observed in the photonic Morpho nanostructures. This mechanism of selective vapor response brings a multivariable perspective for sensing, where selectivity is achieved within a single chemically graded nanostructured sensing unit, rather than from an array of separate sensors.

Characterization of poly(sodium styrene sulfonate) thin films grafted from functionalized titanium surfaces.

Biointegration of titanium implants in the body is controlled by their surface properties. Improving surface properties by coating with a bioactive polymer is a promising approach to improve the biological performance of titanium implants. To optimize the grafting processes, it is important to fully understand the composition and structure of the modified surfaces. The main focus of this study is to provide a detailed, multitechnique characterization of a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film grafted from titanium surfaces via a two-step procedure. Thin titanium films (∼50 nm thick with an average surface roughness of 0.9 ± 0.2 nm) prepared by evaporation onto silicon wafers were used as smooth model substrates. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that the titanium film was covered with a TiO(2) layer that was at least 10 nm thick and contained hydroxyl groups present at the outermost surface. These hydroxyl groups were first modified with a 3-methacryloxypropyltrimethoxysilane (MPS) cross-linker. XPS and ToF-SIMS showed that a monolayer of the MPS molecules was successfully attached onto the titanium surfaces. The pNaSS film was grafted from the MPS-modified titanium through atom transfer radical polymerization. Again, XPS and ToF-SIMS were used to verify that the pNaSS molecules were successfully grafted onto the modified surfaces. Atomic force microscopy analysis showed that the film was smooth and uniformly covered the surface. Fourier transform infrared spectroscopy indicated that an ordered array of grafted NaSS molecules were present on the titanium surfaces. Sum frequency generation vibration spectroscopy and near edge X-ray absorption fine structure spectroscopy illustrated that the NaSS molecules were grafted onto the titanium surface with a substantial degree of orientational order in the styrene rings.

Method for determining the elemental composition and distribution in semiconductor core-shell quantum dots.

In the biological sciences, the use of core-shell quantum dots (QDs) has gained wide usage but analytical challenges still exist for characterizing the QD structure. The application of energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy (XPS) to bulk materials is relatively straightforward; however, for meaningful applications of surface science techniques to multilayer nanoparticles requires novel modifications and analysis methods. To experimentally characterize the elemental composition and distribution in CdSe/CdS/ZnS QDs, we first develop a XPS signal subtraction technique capable of separating the overlapped selenium 3s (core) and sulfur 2s (shell) peaks (both peaks have binding energies near 230 eV) with higher precision than is typically reported in the nanoparticle literature. This method is valid for any nanoparticle containing selenium and sulfur. Then we apply a correction formula to the XPS data and determine that the 2 nm stoichiometric CdSe core is surrounded by 2 CdS layers and a stoichimetric ZnS monolayer. These findings and the multiapproach methodology represent a significant advancement in the detailed surface science study of multilayer nanoparticles. In agreement with recent surprising findings, the time-of-flight secondary mass spectrometry measurements suggest that the surface sites of the QDs used in this study are primarily covered with a mixture of octadecylphosphonic acid and trioctylphophine oxide.

A simple and scalable route to wafer-size patterned graphene.

Producing large-scale graphene films with controllable patterns is an essential component of graphene-based nanodevice fabrication. Current methods of graphene pattern preparation involve either high cost, low throughput patterning processes or sophisticated instruments, hindering their large-scale fabrication and practical applications. We report a simple, effective, and reproducible approach for patterning graphene films with controllable feature sizes and shapes. The patterns were generated using a versatile photocoupling chemistry. Features from micrometres to centimetres were fabricated using a conventional photolithography process. This method is simple, general, and applicable to a wide range of substrates including silicon wafers, glass slides, and metal films.