Jan-Henrik Smått

Probing the phosphoproteome of HeLa cells using nanocast metal oxide microspheres for phosphopeptide enrichment.

Metal oxide affinity chromatography (MOAC) has become a prominent method to enrich phosphopeptides prior to their analysis by liquid chromatography-mass spectrometry. To overcome limitations in material design, we have previously reported the use of nanocasting as a means to generate metal oxide spheres with tailored properties. Here, we report on the application of two oxides, tin dioxide (stannia) and titanium dioxide (titania), for the analysis of the HeLa phosphoproteome. In combination with nanoflow LC-MS/MS analysis on a linear ion trap-Fourier transform ion cyclotron resonance instrument, we identified 619 phosphopeptides using the new stannia material, and 896 phosphopeptides using titania prepared in house. We also compared the newly developed materials to commercial titania material using an established enrichment protocol. Both titania materials yielded a comparable total number of phosphopeptides, but the overlap of the two data sets was less than one-third. Although fewer peptides were identified using stannia, the complementarity of SnO(2)-based MOAC could be shown as more than 140 phosphopeptides were exclusively identified by this material.

Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation

Cellulose nanocrystals (CNCs) as a renewable and biodegradable nanomaterial have wide application value. In this work, CNCs were extracted from bleached chemical pulp using two stages of isolation (i.e. formic acid (FA) hydrolysis and 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) mediated oxidation) under mild conditions. In the first stage, FA was used to remove hemicellulose, swell cellulose fibers, and release CNCs. The FA could be readily recovered and reused. In the second stage, the CNCs isolated by FA were further modified by TEMPO-mediated oxidation to increase the surface charge of CNCs. It was found that the modified CNCs with more ordered crystal structure and higher surface charge had better redispersibility and higher viscosity in aqueous phase. Therefore, the modified CNCs could be more effective when used as rheology modifier in the fields of water based coating, paint, food etc.

Investigation of plasmonic gold–silica core–shell nanoparticle stability in dye-sensitized solar cell applications

Plasmonic core-shell Au@SiO2 nanoparticles have previously been shown to enhance the performance of dye-sensitized solar cells (DSSCs). A thin silica coating can provide a better stability during thermal processing and chemical stability to survive the corrosive electrolyte used in DSSCs. However, the thickness and completeness of the silica shell has proven crucial for the performance of the plasmonic particles and is largely controlled by the linking chemistry between the gold core and silica shell. We have evaluated four different silica coating procedures of ∼15 nm gold nanoparticles for usage in DSSCs. The chemical stability of these core-shell nanoparticles was assessed by dispersing the particles in iodide/triiodide electrolyte solution and the thermal stability by heating the particles up to 500°C. In order to maintain stable gold cores a complete silica coating was required, which was best obtained by using a mercaptosilane as a linker. In situ TEM characterization indicated that the heating process only had minor effects on the core-shell particles. The final step was to evaluate how the stable Au@SiO2 nanoparticles were influencing a real DSSC device when mixed into the TiO2 photoanode. The plasmon-incorporated DSSCs showed a ∼10% increase in efficiency compared to devices without core-shell nanoparticles.

Optimizing the performance of tin dioxide microspheres for phosphopeptide enrichment

Phosphopeptide enrichment based on metal oxide affinity chromatography is one of the most powerful tools for studying protein phosphorylation on a large scale. To complement existing metal oxide sorbents, we have recently introduced tin dioxide as a promising alternative. The preparation of SnO(2) microspheres by the nanocasting technique, using silica of different morphology as a template, offers a strategy to prepare materials that vary in their particle size and their porosity. Here, we demonstrate how such stannia materials can be successfully generated and their properties fine-tuned in order to obtain an optimized phosphopeptide enrichment material. We combined data from liquid chromatography-mass spectrometry experiments and physicochemical characterization, including nitrogen physisorption and energy-dispersive X-ray spectroscopy (EDX), to explain the influence of the various experimental parameters.

Comparison of different amino-functionalization procedures on a selection of metal oxide microparticles: degree of modification and hydrolytic stability.

Amino-modified metal oxide materials are essential in a wide range of applications, including chromatography, ion adsorption, and as biomaterials. The aim of this study is to compare different functionalization techniques on a selection of metal oxides (SiO(2), TiO(2), ZrO(2), and SnO(2)) in order to determine which combination has the optimal properties for a certain application. We have used the nanocasting approach to synthesize micrometer-sized TiO(2), ZrO(2), and SnO(2) particles, which have similar morphologies and porosities as the starting mesoporous SiO(2) microparticles (Lichroprep Si 60). These metal oxides were subsequently functionalized by four different approaches, (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine (AZ), and (d) electrostatic interaction of poly(ethylenimine) (PEI), to produce a high surface coverage of amino groups on their surfaces. Scanning electron microscopy, nitrogen physisorption, and X-ray diffraction were used to characterize the unmodified metal oxide particles, while thermogravimetric analysis, ninhydrin adsorption, and ζ potential titrations were applied to gain insight into the successfulness of the various surface modifications. Finally, the hydrolytic stability at pH 2 and 10 was investigated by ζ potential measurements. Unfortunately, the AEDP approach was not able to produce efficient amino-modification on any of the tested metal oxide surfaces. On the other hand, modifications with APTES, aziridine, and PEI appeared to give fairly stable amino-functionalizations at high pH values for all metal oxides, while these modifications were easily detached at pH 2, with the exception of SnO(2), where the AZ and PEI samples were stable up to 40 h. The results are expected to give valuable insights into the possibility of replacing amino-modified silica with more hydrolytically stable metal oxides in various application fields, for example, chromatography and drug delivery.

Template‐Free Sol‐Gel Synthesis of Hierarchically Macro‐ and Mesoporous Monolithic TiO2

Monolithic titania exhibiting a hierarchical, bimodal meso‐macroporosity has been prepared through a template free sol‐gel synthesis route. The macropore diameter can be controllably varied in the range 0.4–4 µm still maintaining a narrow pore size distribution. The macropores form as a consequence of parallel gelation and microscopic phase separation, where their relative kinetics determine the macropore diameter. We utilize the chelating property of acetic acid to control the kinetics of the reaction, which allows the synthesis to be carried out without the addition of otherwise commonly used hydrogen‐bonding polymers or surfactants. The synthesis is thus both interesting from an economical and an environmental point of view. In addition to macropores, the monoliths also contain textural mesopores, which makes the monoliths interesting for chromatographic and catalytic applications.

Effect of a large hole reservoir on the charge transport in TiO2/organic hybrid devices.

We have fabricated hybrid devices in the form of indium tin oxide/titanium dioxide/poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester/copper (ITO/TiO(2)/P3HT:PCBM/Cu) to clarify the impact of the TiO(2)/P3HT:PCBM interface on the charge transport using the charge extraction by linearly increasing voltage (CELIV) technique. We found that a large equilibrium charge reservoir is accumulated at negative offsets at the TiO(2)/P3HT:PCBM interface leading to space charge limited extraction current (SCLC) transients. We show analytically the SCLC transient response and compare the experimental data to calculated SCLC at a linearly increasing voltage. The theoretical calculations indicate that the large charge reservoir at negative offset voltages is due to thermally generated charges combined with poor hole extraction at the ITO/TiO(2) contact, due to the hole blocking character of TiO(2).

Hierarchical inorganic nanopatterning (INP) through direct easy block-copolymer templating

We introduce a simple route towards hierarchical TiO2 nanopatterns using a block-copolymer template approach combined with a dip-coating process and soft inorganic chemistry. The bimodal characteristic is associated to the preparation of solutions that contain two distinct populations of micelles PB-b-PEO (with the same chemical nature but different sizes) that do not mix or aggregate. The relative quantity of each population can be precisely adjusted in the initial solution composition by mixing the corresponding proportion of parent solutions, and is recovered in the final TiO2 nanopattern. The latter hierarchical nanopatterning exhibits homogeneous distribution of 2 distinct sizes of nanoperforations in relation to the presence of both micelles. We show that the bimodal micellar solution is stable for more than four weeks at RT, revealing an unexpected dynamic stability. We believe that the resulting nanopatterns could be useful for investigating the behaviour of block copolymer micelles in solutions. The present study is mainly supported by DLS and AFM analyses.

Phospholipids covalently attached to silica particles as stationary phase in nano-liquid chromatography

Silica particles were covalently modified with phospholipids and used as packing material for nano-liquid chromatography (nano-LC). This modification involved aminopropylsilylation of the raw silica particles using 3-(aminopropyl)-triethoxysilane, covalent binding of glutaraldehyde molecules to the aminopropylsilylated particles, and finally covalent binding of different phospholipid vesicles containing primary amino groups to the iminoaldehyde silica particles. Capillaries with an inner diameter of 100μm were packed with phospholipid-coated silica particles using a slurry packing method. The packed capillaries were tested in nano-LC with UV-detection for the separation of acidic, neutral, and basic model analytes. The effect of the buffer ion on the retention factor of the analytes was evaluated using buffer solutions with constant ionic strength and pH. In addition, the effect of the volume of methanol in the mobile phase was studied. The calculated distribution coefficients (logK(D)) of the model compounds were in agreement with those reported in the literature. A good correlation between logK(D) values and octanol/water partitioning coefficients (P(o/w)) for neutral hydrophobic analytes was obtained proving the applicability of the method for predicting partitioning of the compounds with the biomembranes.

Polyethylenimine-modified metal oxides for fabrication of packed capillary columns for capillary electrochromatography and capillary liquid chromatography.

The need for novel packing materials in both capillary electrochromatography (CEC) and capillary liquid chromatography (CLC) is apparent and the development towards more selective, application-oriented chromatographic phases is under progress world-wide. In this study we have synthesized new polyethyleneimine (PEI) functionalized Mn(2)O(3), SiO(2), SnO(2), and ZrO(2) particles for the fabrication of packed capillary columns for CEC and CLC. The nanocasting approach was successful for the preparation of functionalized metal oxide materials with a controlled porosity and morphology. PEI functionalization was done using ethyleneimine monomers to create particles which are positively charged in aqueous solution below pH 9. This functionalization allowed the possibility to have both hydrophobic (due to its alkyl chain) and ionic interactions (due to positively charged amino groups) with selected compounds. For comparison aminopropyl-functionalized silica was also synthesized and tested. Both slurry pressure and electrokinetic packing procedures used gave similar results, but fast sedimentation of the material caused some problems during the packing. The high stability and wide pH range of PEI-functionalized SiO(2) material, with potential for hydrophobic and electrostatic interactions, proved to be useful for the CEC and CLC separation of some model acidic and neutral compounds.