Development of a facile method to compute collagen network pathological anisotropy using AFM imaging.

Type I collagen, a fundamental extracellular matrix (ECM) component, is pivotal in maintaining tissue integrity and strength. It is also the most prevalent fibrous biopolymer within the ECM, ubiquitous in mammalian organisms. This structural protein provides essential mechanical stability and resilience to various tissues, including tendons, ligaments, skin, bone, and dentin. Collagen has been structurally investigated for several decades, and variation to its ultrastructure by histology has been associated with several pathological conditions. The current study addresses a critical challenge in the field of collagen research by providing a novel method for studying collagen fibril morphology at the nanoscale. It offers a computational approach to quantifying collagen properties, enabling a deeper understanding of how collagen type I can be affected by pathological conditions. The application of Fast Fourier Transform (FFT) coupled with Atomic Force Microscope (AFM) imaging distinguishes not only healthy and diseased skin but also holds potential for automated diagnosis of connective tissue disorders (CTDs), contributing to both clinical diagnostics and fundamental research in this area. Here we studied the changes in the structural parameters of collagen fibrils in Ehlers Danlos Syndrome (EDS). We have used skin extracted from genetically mutant mice that exhibit EDS phenotype as our model system (Col1a1Jrt/+ mice). The collagen fibrils were analyzed by AFM based descriptive-structural parameters, coupled with a 2D Fast Fourier Transform(2D-FFT) approach that automated the analysis of AFM images. In addition, each sample was characterized based on its FFT and power spectral density. Our qualitative data showed morphological differences in collagen fibril clarity (clearness of the collagen fibril edge with their neighbouring fibri), D-banding, orientation, and linearity. We have also demonstrated that FFT could be a new tool for distinguishing healthy from tissues with CTDs by measuring the disorganization of fibrils in the matrix. We have also employed FFT to reveal the orientations of the collagen fibrils, providing clinically relevant phenotypic information on their organization and anisotropy. The result of this study can be used to develop a new automated tool for better diagnosis of CTDs.

Violin Varnishes: Microstructure and Nanomechanical Analysis.

The aim of the current work is twofold: to demonstrate the application of in situ non-invasive imaging by portable atomic force microscopy (AFM) on the surfaces of a violin and to integrate compositional and mechanical analysis at the nano scale level on model samples of varnished wood. These samples were prepared according to traditional recipes by an Italian lute-maker family well practised in the art. Samples of oil and spirit-based varnishes on maple wood, naturally and accelerated light aged, were studied. AFM was used to measure the nanomechanical properties of the model samples and established that the spirit-based varnish was stiffer than the oil-based. Synchrotron radiation micro- Fourier Transform Infra-red analysis of the layer structure revealed that stiffer spirit-based varnish showed less penetration into the wood than the oil-based. Further PeakForce Quantitative Nanomechanical Mapping (QNM) demonstrated a difference in adhesion values between the oil- and spirit-based samples.

Compromised dental cells viability following teeth-whitening exposure.

This study aimed to assess the viability of dental cells following time-dependent carbamide peroxide teeth-whitening treatments using an in-vitro dentin perfusion assay model. 30 teeth were exposed to 5% or 16% CP gel (4 h daily) for 2-weeks. The enamel organic content was measured with thermogravimetry. The time-dependent viability of human dental pulp stem cells (HDPSCs) and gingival fibroblast cells (HGFCs) following either indirect exposure to 3 commercially available concentrations of CP gel using an in-vitro dentin perfusion assay or direct exposure to 5% H2O2 were investigated by evaluating change in cell morphology and by hemocytometry. The 5% and 16% CP produced a significantly lower (p < 0.001) enamel protein content (by weight) when compared to the control. The organic content in enamel varied accordingly to the CP treatment: for the 16% and 5% CP treatment groups, a variation of 4.0% and 5.4%, respectively, was observed with no significant difference. The cell viability of HDPSCs decreased exponentially over time for all groups. Within the limitation of this in-vitro study, we conclude that even low concentrations of H2O2 and CP result in a deleterious change in enamel protein content and compromise the viability of HGFCs and HDPSCs. These effects should be observed in-vivo.

Controlled Environment Neutron Radiography of Moisture Sorption/Desorption in Nanocellulose-Treated Cotton Painting Canvases.

Nanocellulose-based materials have recently been used to consolidate degraded cotton painting canvases. Canvas-supported paintings consist of materials that are sensitive to moisture and especially susceptible to environmental fluctuations in temperature and relative humidity (RH). These environmental fluctuations occur in uncontrolled environments found in historic houses and palaces and can lead to hydrolytic degradation and mechanical damage to canvases. To simulate this situation in an experimental setting, canvas samples were mounted in a custom-made closed-cell and subjected to programmed cycles of RH at a controlled temperature while exposed to the neutron beam. Results are presented for both untreated samples and those treated with a polar consolidant, cellulose nanofibrils (CNF(aq)) in water, and an apolar consolidant, a composite of persilylated methyl cellulose with surface silylated cellulose nanocrystals (MC+CNC(h)) in heptane. They were then compared with changes in ionic conductivities as measured by dielectric analysis (DEA) with the same cyclic RH program and temperature. Although the samples were exposed to the same experimental conditions, they presented treatment-specific responses. CNF-treated canvas showed higher hygroscopicity than the untreated sample and facilitated moisture diffusion across the sample to areas not exposed to the environment. A sample treated with MC+CNC(h) retarded moisture diffusion during the increase in RH and could, therefore, afford protection to moisture absorption in uncontrolled environments. Thus, the experimental setup and resulting data provide a pilot study demonstrating the potential of neutron radiography in following and comparing real-time moisture diffusion dynamics in untreated and nanocellulose-consolidated cotton canvases and assisting in validating the overall benefit of the treatment.

Evaluation of the Adhesion and Performance of Natural Consolidants for Cotton Canvas Conservation.

Recent developments in paper and canvas conservation have seen the introduction of nanocellulose (NC) as a compatible treatment for the consolidation of historical cellulosic artifacts and manuscripts. However, as part of the assessment of these new materials for canvas consolidation, the adhesion of the consolidation treatment (which takes place between the applied material and the substrate) has not yet been evaluated, and as a result, it is poorly understood by both the scientific and conservation communities. After evaluating the potential of NC treatments for the consolidation of cotton painting canvas, we investigate a route to promote the interaction between the existing canvas and the nanocellulose treatment, which is in our case made of cellulose nanofibrils (CNF). This was carried out by introducing a cationic polymer, polyamidoamine-epichlorohydrin (PAAE), as an intermediate layer between the canvas and the CNF. The morphological, chemical, and mechanical evaluation of the canvas samples at different relative humidity (RH) levels demonstrated how the adhesion of the added PAAE layer is a dominant factor in the consolidation process. Improvement in the coating of canvas single fibers by the CNF, higher adhesion energy between the canvas fibers and the CNF treatment, and finally overall stronger canvas reinforcement were observed following the introduction of PAAE. However, an increase in mechanical response to moisture sorption and desorption was also observed for the PAAE-treated canvases. Overall, this study shows the complexity of such systems and, as such, the relevance of using a multiscale approach for their assessment.

On the potential of using nanocellulose for consolidation of painting canvases.

Nanocellulose has been recently proposed as a novel consolidant for historical papers. Its use for painting canvas consolidation, however, remains unexplored. Here, we show for the first time how different nanocelluloses, namely mechanically isolated cellulose nanofibrils (CNF), carboxymethylated cellulose nanofibrils (CCNF) and cellulose nanocrystals (CNC), act as a bio-based alternative to synthetic resins and other conventional canvas consolidants. Importantly, we demonstrate that compared to some traditional consolidants, all tested nanocelluloses provided reinforcement in the adequate elongation regime. CCNF showed the best consolidation per added weight; however, it had to be handled at very low solids content compared to other nanocelluloses, exposing canvases to larger water volumes. CNC reinforced the least per added weight but could be used in more concentrated suspensions, giving the strongest consolidation after an equivalent number of coatings. CNF performed between CNC and CCNF. All nanocelluloses showed better consolidation than lining with synthetic adhesive (Beva 371) and linen canvas in the elongation region of interest.

Remote assessment of cultural heritage environments with wireless sensor array networks.

The logistics and cost of environmental monitoring can represent challenges for heritage managers, partly because of the sheer number of environmental parameters to consider. There is a need for a system, capable of monitoring the holistic impact of the environment on cultural materials while remaining relatively easy to use and providing remote access. This paper describes a dosimetric system based on piezoelectric quartz crystal technology. The prototype sensing module consists of an array of piezoelectric quartz crystals (PQC) coated with different metals (Fe, Cu, Ni and Sn) and includes a temperature and relative humidity sensor. The communication module involves an 802.15.4 low-power radio and a GPRS gateway which allows real time visualisation of the measurements online. An energy management protocol ensures that the system consumes very low power between measurements. The paper also describes the results and experiences from two heritage field deployments, at Apsley House in London, UK, and at the Royal Palaces of Abomey in Benin. Evaluation of PQC measurements, temperature, relative humidity and the rate of successful transmission over the communication systems are also reported.

Effects of photochemical riboflavin-mediated crosslinks on the physical properties of collagen constructs and fibrils.

The use of collagen scaffold in tissue engineering is on the rise, as modifications to mechanical properties are becoming more effective in strengthening constructs whilst preserving the natural biocompatibility. The combined technique of plastic compression and cross-linking is known to increase the mechanical strength of the collagen construct. Here, a modified protocol for engineering these collagen constructs is used to bring together a plastic compression method, combined with controlled photochemical crosslinking using riboflavin as a photoinitiator. In order to ascertain the effects of the photochemical crosslinking approach and the impact of the crosslinks created upon the properties of the engineered collagen constructs, the constructs were characterized both at the macroscale and at the fibrillar level. The resulting constructs were found to have a 2.5 fold increase in their Young's modulus, reaching a value of 650 ± 73 kPa when compared to non-crosslinked control collagen constructs. This value is not yet comparable to that of native tendon, but it proves that combining a crosslinking methodology to collagen tissue engineering may offer a new approach to create stronger, biomimetic constructs. A notable outcome of crosslinking collagen with riboflavin is the collagen's greater affinity for water; it was demonstrated that riboflavin crosslinked collagen retains water for a longer period of time compared to non-cross-linked control samples. The affinity of the cross-linked collagen to water also resulted in an increase of individual collagen fibrils' cross-sectional area as function of the crosslinking. These changes in water affinity and fibril morphology induced by the process of crosslinking could indicate that the crosslinked chains created during the photochemical crosslinking process may act as intermolecular hydrophilic nanosprings. These intermolecular nanosprings would be responsible for a change in the fibril morphology to accommodate variable volume of water within the fibril.

The role of organic and inorganic indoor pollutants in museum environments in the degradation of dammar varnish.

This paper investigates the effects of inorganic (NO(2) and O(3)) and volatile organic acid (acetic acid) pollutants on the degradation of dammar varnish in museum environments. Model paint varnish samples based on dammar resin were investigated by Gas Chromatography Mass Spectrometry (GC-MS), Dynamic Mechanical Analysis (DMA) and Atomic Force Microscopy (AFM). Dammar is a natural triterpenoid resin, commonly used as a paint varnish. Samples were subjected to accelerated ageing by different levels of pollutants (NO(2) and O(3) and acetic acid) over a range of relative humidities (RH) and then analysed. The results revealed that as the dose of the pollutant was increased, so did the degree of oxidation and cross-linking of the resin. Most interestingly, it was shown for the first time that exposure to acetic acid vapour resulted in the production of an oxidised and cross-linked resin, comparable to the resin obtained under exposure to NO(2) and O(3). These conclusions were supported by the analyses of model varnishes exposed for about two years in selected museum environments, where the levels of pollutants had been previously measured. Exposures were performed both within and outside the selected microclimate frames for paintings. Results showed that varnishes placed within the microclimate frames were not always better preserved than those exposed outside the frames. For some sites, the results highlighted the protective effects of the frames from outdoor generated pollutants, such as NO(2) and O(3). For other sites, the results showed that the microclimate frames acted as traps for the volatile organic acids emitted by the wooden components of the mc-frames, which damaged the varnish.

A sutureless aortic stent-graft based on a nitinol scaffold bonded to a compliant nanocomposite polymer is durable for 10 years in a simulated in vitro model.

PURPOSE: To physiologically test the durability of a sutureless aortic stent-graft based on nitinol bonded to polyhedral oligomeric silsesquioxane (POSS) and poly(carbonate-urea) urethane (PCU) for 10 years according to Food and Drug Administration guidelines. METHODS: Aortic stent-grafts (n = 4) were tested in 37°C distilled water using simulated in vivo hydrodynamic pulse loading. After 400 million cycles, surface topography was assessed by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. Dynamic compliance was measured using a pulsatile flow phantom. Mechanical and elastic properties were determined by stress-strain studies and elastic deformation tests. Dynamic scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to assess thermal resistance. Comparison was made with a zero-cycled control. RESULTS: All stent-grafts successfully completed accelerated pulsatile fatigue at 94±14-mmHg pulse pressure. SEM images confirmed uniform surface topography without any fractures. FTIR showed increased intensity of -NHCO- bonds, but there was no significant sign of biodegradation. Tensile stress of fatigue-tested polymer compared favorably with the zero-cycled control at 50% to 500% strain (p = 0.69). At a mean pressure range of 60 to 120 mmHg, overall compliance of the fatigue-tested grafts was 3.48±1.27%mmHg(-1)×10(-2) with no significant difference compared to control (3.26±0.65%mmHg(-1)×10(-2); p = 0.47). DSC and TMA showed comparable thermotropic transition. CONCLUSION: Simulated physiological in vivo hydrodynamic loading has no significant degradative effect on an innovative sutureless stent-graft made from POSS-PCU nanocomposite polymer. Sutureless technology incorporating nitinol stents proved to be robust, with no separation over an accelerated 10-year cycle, which may allow development of durable stent-grafts with better compliance.

Thermal denaturation studies of collagen by microthermal analysis and atomic force microscopy.

The structural properties of collagen have been the subject of numerous studies over past decades, but with the arrival of new technologies, such as the atomic force microscope and related techniques, a new era of research has emerged. Using microthermal analysis, it is now possible to image samples as well as performing localized thermal measurements without damaging or destroying the sample itself. This technique was successfully applied to characterize the thermal response between native collagen fibrils and their denatured form, gelatin. Thermal transitions identified at (150 ± 10)°C and (220 ± 10)°C can be related to the process of gelatinization of the collagen fibrils, whereas at higher temperatures, both the gelatin and collagen samples underwent two-stage transitions with a common initial degradation temperature at (300 ± 10)°C and a secondary degradation temperature of (340 ± 10)°C for the collagen and of (420 ± 10)°C for the gelatin, respectively. The broadening and shift in the secondary degradation temperature was linked to the spread of thermal degradation within the gelatin and collagen fibrils matrix further away from the point of contact between probe and sample. Finally, similar measurements were performed inside a bone resorption lacuna, suggesting that microthermal analysis is a viable technique for investigating the thermomechanical response of collagen for in situ samples that would be, otherwise, too challenging or not possible using bulk techniques.

Characterisation of temperature-dependent phase transitions in 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazene, N3P3Cl4[O(CH2)3O].

BACKGROUND: The crystal structure of 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclo triphosphazene has been determined at 120, 274 and 293 K. The result at 293 K confirms the room temperature Cmc2(1) structure, but at the lower temperatures the space group is Pna2(1). Nevertheless the basic structure remains the same, with only small displacements of the atoms, amounting to an average of 25 pm between 120 and 293 K. RESULTS: X-ray diffraction and DSC results indicate that the phase transition takes place in two steps between 274 - 293 K and provides an understanding of previous NQR results. In the intermediate temperature range the molecules are displaced from their room temperature positions in such a way as to give an average structure with Cmc2(1) symmetry. CONCLUSION: The overall phase transition is consistent with the occurrence of a soft lattice mode at room temperature in which a large displacement of the molecule in the x-direction is coupled with a flexing motion about an axis defined by the nitrogen atoms in the N1 and N3 positions.

Silsesquioxane nanocomposites as tissue implants.

BACKGROUND: Silicone implants are being used increasingly worldwide, especially in breast augmentation procedures. The most common morbidity observed is capsular contracture, which occurs in 15 percent of cases. To overcome this problem, the authors have developed a novel nanocomposite based on polyhedral oligomeric silsesquioxane-poly(carbonate-urea)urethane (POSS-PCU) for use as tissue implants. METHODS: These polymers were implanted in six healthy sheep (n = 6) for 36 months and a siloxane served as the positive control. After explantation, these polymers were extracted, as was the surrounding capsule, if any. Attenuated total reflectance Fourier transform infrared spectroscopy analysis was performed to look for signs of surface degradation on the polymers and histopathologic and electron microscopic examinations were performed to study the interaction between the biomaterial and the host environment in greater detail. RESULTS: After implantation, the authors observed minimal inflammation of the nanocomposite within the sheep model as compared with the siloxane control. Contact angle measurements and fibrinogen enzyme-linked immunosorbent assay tests were then conducted on the POSS-PCU nanocomposite to determine the reason for this behavior. The increased fibrinogen adsorption on POSS-PCU, its amphilicity, and large contact-angle hysteresis indicated that POSS-PCU inhibits inflammation by adsorbing and inactivating fibrinogen on its surface. In complete contrast, the control siloxane in the same setting demonstrated very significant inflammation and degradation, resulting in capsular formation. Naturally, there was no evidence of degradation of the nanocomposite compared with the siloxane control. CONCLUSIONS: POSS-PCU nanocomposites have enhanced interfacial biocompatibility and better biological stability as compared with conventional silicone biomaterials, thus making them safer as tissue implants.

Analysis and optimization of the cationic lipid component of a lipid/peptide vector formulation for enhanced transfection in vitro and in vivo.

We have previously described a lipopolyplex formulation comprising a mixture of a cationic peptide with an integrin-targeting motif (K16GACRRETAWACG) and Lipofectin, a liposome consisting of DOTMA and DOPE in a 1:1 ratio. The high transfection efficiency of the mixture involved a synergistic interaction between the lipid/peptide components. The aim of this study was to substitute the lipid component of the lipopolyplex to optimize transfection further and to seek information on the structure-activity relationship of the lipids in the lipopolyplex. Symmetrical cationic lipids with diether linkages that varied in alkyl chain length were formulated into liposomes and then incorporated into a lipopolyplex by mixing with an integrin-targeting peptide and plasmid DNA. Luciferase transfections were performed of airway epithelial cells and fibroblasts in vitro and murine lung airways in vivo. The biophysical properties of lipid structures and liposome formulations and their potential effects on bilayer membrane fluidity were determined by differential scanning calorimetry and calcein-release assays. Shortening the alkyl tail from C18 to C16 or C14 enhanced lipopolyplex and lipoplex transfection in vitro but with differing effects. The addition of DOPE enhanced transfection when formulated into liposomes with saturated lipids but was more variable in its effects with unsaturated lipids. A substantial improvement in transfection efficacy was seen in murine lung transfection with unsaturated lipids with 16 carbon alkyl tails. The optimal liposome components of lipopolyplex and lipoplex vary and represent a likely compromise between their differing structural and functional requirements for complex formation and endosomal membrane destabilization.

Review paper: principles and applications of surface analytical techniques at the vascular interface.

Surface properties have been found to be one of the key parameters which cause degradation and of thrombogenicity in all polymers used in biomedical devices, thus signifying the importance and the necessity for quantitative and accurate characterization of the polymer surface itself as used in the construction of the device. The characterization techniques employed generally involve thermal and spectroscopic measurements, in which class the electrochemical investigations and scanning probe microscopies can also be included. Current hypotheses on the correlations that exist between surface parameters and hemocompatibility and degradation of polymers are examined herein, but concentrating on the field of clinically utilized polymeric materials as used within medical devices themselves. Furthermore, this review provides a brief but complete synopsis of these techniques and other emerging ones, which have proven useful in the analysis of the surface properties of polymeric materials as used in the construction of cardiovascular devices. Statements and examples are given as to how specific information can be acquired from these differing methodologies and how it aids in the design and development of new polymers for usage in biomedical device construction.

The degradative resistance of polyhedral oligomeric silsesquioxane nanocore integrated polyurethanes: an in vitro study.

Polymer biostability is one of the critical parameters by which these materials are selected for use as biomedical devices. This is the major rationale for the use of polymers which are highly crystalline and stiff namely expanded polytetrafluoroethylene (ePTFE) and Dacron in particular, as arterial bypass grafts. While this is immaterial in high-flow states, it becomes critically important at lower flows with a greater need for more compliant vessels. Polyurethanes being one of the most compliant polymers known are as such, the natural choice to build such constructs. However, concerns regarding their resistance to degradation have limited their use as vascular prostheses and in order to augment their strength, herein a novel polyhedral oligomeric silsesquioxane integrated poly(carbonate-urea)urethane (POSS-PCU) nanocomposite was synthesised by our group. In the following series of experiments, the POSS-PCU nanocomposite samples were exposed to accelerated degradative solutions, in an 'in-house' established model in vitro for up to 70 days before being subjected to infra-red spectroscopy, scanning electron microscopy, stress-strain studies and differential scanning calorimetry. Our results demonstrate that these silsesquioxane nanocores shield the soft segment(s) of the polyurethane, responsible for its compliance and elasticity from all forms of degradation, principally oxidation and hydrolysis. These nanocomposites hence provide an optimal method by which these polymers may be strengthened whilst maintaining their elasticity, making them ideal as vascular prostheses particularly at low flow states.

Atomic force microscopy of collagen structure in bone and dentine revealed by osteoclastic resorption.

Mineralised tissues such as bone consist of two material phases: collagen protein fibrils, secreted by osteoblasts, form model structures for subsequent deposition of mineral, calcium hydroxyapatite. Collagen and mineral are removed in a three-dimensional manner by osteoclasts during bone turnover in skeletal growth or repair. Bone active drugs have recently been developed for skeletal diseases, and there is revived interest in changes in the structure of mineralised tissues seen in disease and upon treatment. The resolution of atomic force microscopy and use of unmodified samples has enabled us to image bone and dentine collagen exposed by the natural process of cellular dissolution of mineralised matrix. The morphology of bone and dentine has been analysed when fully mineralised and after osteoclast-mediated bone resorption, and compared with results from other microscopy techniques. Banded type I collagen, with 66.5+/-1.4 nm axial D-periodicity and 62.2+/-7.0 nm diameter, has been identified within resorption lacunae in bone and 69.4+/-4.3 nm axial D-periodicity and 140.6+/-12.4 nm diameter in dentine substrates formed by human and rabbit osteoclasts, respectively. This observation suggests a route by which the material and morphological properties of bone collagen can be analysed in situ, compared with collagen from non-skeletal sites, and contrasted in diseases of medical importance, such as osteoporosis, where skeletal tissue is mechanically weakened.

Thermo-mechanical analysis of a compliant poly(carbonate-urea)urethane after exposure to hydrolytic, oxidative, peroxidative and biological solutions.

AIMS: To date, there is still a great need for a fully viable small diameter (< 6 mm) polymeric vascular graft. Currently in such low flow locations, non-elastic expanded polytetrafluoroethylene (ePTFE) is the best available but it is quite inferior to autologous saphenous vein since it fails due to intimal hyperplasia caused by compliance mismatch between the graft and elastic host artery. Recently, a novel compliant poly(carbonate-urea)urethane vascular graft whose trade name is MyoLink has been developed. In this article, we report the findings of a thermo-mechanical analysis of the polymers chemistry postexposure to in vitro solutions comprised of hydrolytic, oxidative, peroxidative and biological media. METHODS AND MATERIALS: The following degradative solutions were used in vitro: plasma fractions I-IV; phospholipase A2 (PLA); cholesterol esterase (CE) and solutions of H2O2/CoCl2, t-butyl peroxide/CoCl2 (t-but/CoCl2) and glutathione/t-butyl peroxide/ CoCl2 (glut/t-but/CoCl2). The MyoLink graft was compared against a conventional poly(ether)urethane (Pulse-Tec). All the graft specimens were 100 mm in length (5.0 mm ID) and were incubated in the latter solutions at 37 degrees C for 70 days in total. The following thermo-mechanical methods were used to analyse both graft types: thermo-mechanical analysis (TMA) and dynamic mechanical thermal analysis (DMTA). RESULTS: Incubation of Pulse-Tec in plasma fractions I-IV, PLA and CE reveals only one observable modification: an increase in the size of the low temperature, melting phase. But incubation in H2O2/CoCl2, and t-but/CoCl2 leads to an increase in the polymeric phase separation coupled with an enlargement in the size of the low temperature melting crystalline phase in Pulse-Tec. The glut/t-but/CoCl2 solution leads to a phase separation between the hard and soft segment domains, coupled with an increase of the internal order within the hard segment domains in Pulse-Tec. The only system in which MyoLink degraded was glut/t-but/CoCl2. In this system, an increase of the phase separation coupled with a simultaneous increase of the crystal size of the low-temperature melting crystalline phase occurred. CONCLUSION: This study shows dramatic changes in the chemistry of the soft and hard segments occurred in the case of the conventional poly(ether)urethane Pulse-Tec graft material. Such changes were not manifested in the majority of solutions in the case of MyoLink but a hydrolytic-led degradation of the carbonate soft segment was evidenced only in the glut/t-but/CoCl2 system.