The aim of this paper is twofold: first to report on the lateral and vertical characterisation of a surface chemical gradient of carboxylic-acid functionality and second, to demonstrate the use of said gradient to probe the passive adsorption of immunoglobulin G (IgG) as a function of the density of surface carboxylic-acid groups.A surface chemical gradient of carboxylic-acid functionality was fabricated by the plasma copolymerisation of octadiene (OD) and acrylic acid (AA). The plasma-polymerised gradient was over 12 mm, with 2 mm of plasma-polymerised OD at one end and 2 mm of plasma-polymerised AA at the other. By means of linescan angle resolved x-ray photoelectron spectroscopy (ARXPS) it is shown precisely how acid functionality varies from the 2 mm position (OD end) on the gradient to the 10 mm position (AA end). By recording data from 16 angles at each of the 25 sampling points along the gradient, it is shown that the surface gradient also changes vertically, most notably in the thickness of the plasma polymer. At the OD end the plasma-polymerised layer is 6.3 nm thick, while at the AA end the plasma-polymerised layer is 5 nm. More subtle changes in chemistry through the plasma-polymerised layer are shown at the 7.5 and 10 mm points.An identical gradient is used to probe IgG adsorption along the length of the gradient. ARXPS is used to monitor the nitrogen 1s (N1s) signal at 25 points, the N1s signal being unique to adsorbed IgG. It is demonstrated that IgG adsorbs in far greater amount (IgG per unit area) at the OD end, and the amount of adsorbed IgG decreases along the length of the gradient. It is estimated that >200 ng/cm 2 adsorbed at the OD, while at the AA the amount adsorbed was <20 ng/cm 2 .

A gradient of functional heparin is fabricated onto a surface chemical gradient of plasma‐polymerized allyl amine (see figure). While heparin functionality changes across the gradient, increased adsorption of heparin onto the surface is not accompanied with a continued, corresponding rise in heparin function.

Mouse embryonic stem cells (mESCs) undergo self-renewal in the presence of the cytokine, leukaemia inhibitory factor (LIF). Following LIF withdrawal, mESCs differentiate, and this is accompanied by an increase in cell–substratum adhesion and cell spreading. The purpose of this study was to investigate the relationship between cell spreading and mESC differentiation. Using E14 and R1 mESC lines, we have restricted cell spreading in the absence of LIF by either culturing mESCs on chemically defined, weakly adhesive biomaterial substrates, or by manipulating the cytoskeleton. We demonstrate that by restricting the degree of spreading by either method, mESCs can be maintained in an undifferentiated and pluripotent state. Under these conditions, self-renewal occurs without the need for LIF and is independent of nuclear translocation of tyrosine-phosphorylated STAT3 or β-catenin, which have previously been implicated in self-renewal. We also demonstrate that the effect of restricted cell spreading on mESC self-renewal is not mediated by increased intercellular adhesion, as evidenced by the observations that inhibition of mESC adhesion using a function blocking anti E-cadherin antibody or siRNA do not promote differentiation. These results show that mESC spreading and differentiation are regulated both by LIF and by cell–substratum adhesion, consistent with the hypothesis that cell spreading is the common intermediate step in the regulation of mESC differentiation by either LIF or cell–substratum adhesion.

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Film stability of functionalised plasma polymer (PP) films in aqueous environments is an issue. Whilst methods are routinely employed to enhance aqueous stability, the issue itself has not previously been systematically studied. Herein, we describe a method using gradient PP surfaces whereby aqueous stability can be explored as a function of PP composition and substratum. X‐ray photoelectron spectroscopy (XPS) is used to examine PP films on glass and Thermanox “as‐prepared” and post‐immersion (24 h) in distilled H2O. Our data indicate stability becomes an issue with increase in functionalisation, but that functionalised PPs are much more stable when deposited on polymeric Thermanox than when deposited onto glass. Substratum influence in PP films thicker than the XPS sampling depth is a surprise.