Stress relaxation analysis of single chondrocytes using porohyperelastic model based on AFM experiments

The aim of this study is to investigate the stress relaxation behavior of single chondrocytes using the Porohyperelastic (PHE) model and inverse Finite Element Analysis (FEA). Firstly, based on Atomic Force Microscopy (AFM) technique, we have found that the chondrocytes exhibited stress relaxation behavior. We explored the mechanism of this stress relaxation behavior and concluded that the intracellular fluid exuding out from the cells during deformation plays the most important role in the stress relaxation. Next, we have applied the inverse FEA technique to determine necessary material parameters for PHE model to simulate this stress relaxation behavior as this model is proven capable of capturing the non-linear behavior and the fluid-solid interaction during the stress relaxation of the single chondrocytes. It is observed that this PHE model can precisely capture the stress relaxation behavior of single chondrocytes and would be a suitable model for cell biomechanics.

Nanomorphology influence on the light conversion mechanisms in highly efficient diketopyrrolopyrrole based organic solar cells

In this work, diketopyrrolopyrrole-based polymer bulk heterojunction solar cells with inverted and regular architecture have been investigated. The influence of the polymer:fullerene ratio on the photoactive film nanomorphology has been studied in detail. Transmission Electron Microscopy and Atomic Force Microscopy reveal that the resulting film morphology strongly depends on the fullerene ratio. This fact determines the photocurrent generation and governs the transport of free charge carriers. Slight variations on the PCBM ratio respect to the polymer show great differences on the electrical behavior of the solar cell. Once the polymer:fullerene ratio is accurately adjusted, power conversion efficiencies of 4.7% and 4.9% are obtained for inverted and regular architectures respectively. Furthermore, by correlating the optical and morphological characterization of the polymer:fullerene films and the electrical behavior of solar cells, an ad hoc interpretation is proposed to explain the photovoltaic performance as a function of this polymer:blend composition.

A fluorenone based low band gap solution processable copolymer for air stable and high mobility organic field effect transistors

A fluorenone based alternating copolymer (PFN-DPPF) with a furan based fused aromatic moiety has been designed and synthesized. PFN-DPPF exhibits a small band gap with a lower HOMO value. Testing this polymer semiconductor as the active layer in organic thin-film transistors results in hole mobilities as high as 0.15 cm2 V-1 s-1 in air.

A low-bandgap diketopyrrolopyrrole-benzothiadiazole-based copolymer for high-mobility ambipolar organic thin-film transistors

A new, solution-processable, low-bandgap, diketopyrrolopyrrole- benzothiadiazole-based, donor-acceptor polymer semiconductor (PDPP-TBT) is reported. This polymer exhibits ambipolar charge transport when used as a single component active semiconductor in OTFTs with balanced hole and electron mobilities of 0.35 cm2 V-1s-1 and 0.40 cm 2 V-1s-1, respectively. This polymer has the potential for ambipolar transistor-based complementary circuits in printed electronics.

4-hexylbithieno[3,2-b:2′3′-e]pyridine: An efficient electron-accepting unit in fluorene and indenofluorene copolymers for light-emitting devices

4-Hexylbithienopyridine has been prepared as a novel electron-accepting monomer for conjugated polymers. To test its electronic properties, alternating copolymers with fluorene and indenofluorene polymers have been prepared. The copolymers displayed reduction potentials about 0.5 V lower than for the corresponding fluorene and indenofluorene homopolymers, indicating much improved electron-accepting properties. Analysis of the microscopic morphology of thin films of the copolymers by AFM shows that they lack the extensive supramolecular order seen with the homopolymers, which is attributed to the bithienopyridine units disrupting the π-stacking. LEDs using these polymers as the emitting layer produce blue-green emission with low turn-on voltages with aluminum electrodes confirming their improved electron affinity. The indenofluorene copolymer displayed an irreversible red shift in emission at high voltages, which is attributed to oxidation of the indenofluorene units. This red shift occurred at higher potentials than for indenofluorene homopolymers in LEDs, suggesting that the heterocyclic moieties offer some protection against electrically promoted oxidation.

Solid-state assemblies and optical properties of conjugated oligomers combining fluorene and thiophene units

Two conjugated oligomers, representing elementary segments of fluorene-thiophene copolymers, are compared in terms of the microscopic morphology and the optical properties of thin deposits. The atomic force microscopy morphological data and the solid-state absorption and emission spectra are interpreted in terms of the assembly of the conjugated molecules. The compound with a terthiophene central unit and fluorene end-groups shows well-defined monolayer-by-monolayer assembly into micrometer-long stripe-like structures, with a crystalline herringbone-type organization within the monolayers. Polarized confocal microscopy indicates a strong orientation of the crystalline domains within the stripes. In contrast, the compound with a terfluorene central unit and thiophene end groups forms no textured aggregates and the optical spectra in the solid-state are very similar to those recorded in solution, suggesting that the molecules interact only weakly in the solid. The difference in behaviour between the two compounds most probably originates from their different capability to form densely-packed assemblies of interacting π-systems.

Supramolecular organization in fluorene/indenofluorene-oligothiophene alternating conjugated copolymers

A series of conjugated copolymers containing fluorene or indenofluorene units alternating with oligothiophene segments, with potential interest for use as the active layer in field-effect transistors, is investigated. Atomic force microscopy analysis of the morphology of thin deposits shows either the formation of fibrillar structures, which are the signature of long-range π stacking, or the presence of untextured aggregates, resulting from disordered assembly. These morphologies are interpreted in terms of the supramolecular organization of the conjugated chains. Molecular modeling simulations indicate that the commensurability between the lengths of the monomer units and the presence of alkyl side groups are the two key structural factors governing the chain organization into highly ordered assemblies. The most favorable structures are those combining fluorene (indenofluorene) units with unsubstituted bithiophene (terthiophene) segments.

Water-based nanoparticulate solar cells using a diketopyrrolopyrrole donor polymer

Organic photovoltaic devices with either bulk heterojunction (BHJ) or nanoparticulate (NP) active layers have been prepared from a 1:2 blend of (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) (PDPP-TNT) and the fullerene acceptor, ([6,6]-phenyl C71-butyric acid methyl ester) (PC70BM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been used to investigate the morphology of the active layers of the two approaches. Mild thermal treatment of the NP film is required to promote initial joining of the NPs in order for the devices to function, however the NP structure is retained. Consequently, whereas gross phase segregation of the active layer occurs in the BHJ device spin cast from chloroform, the nanoparticulate approach retains control of the material domain sizes on the length scale of exciton diffusion in the materials. As a result, NP devices are found to generate more than twice the current density of BHJ devices and have a substantially greater overall efficiency. The use of aqueous nanoparticulate dispersions offers a promising approach to control the donor acceptor morphology on the nanoscale with the benefit of environmentally- friendly, solution-based fabrication. © 2014 the Owner Societies.

Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces

Electropolymerized films of teraaminometallophthalocyanines (MTAPc; M = Ni and Co) with amino groups at α- (4α-MTAPc) and β- (4β-MTAPc) positions were prepared on glassy carbon (GC) and indium tin oxide (ITO) electrodes. It was found that the electropolymerization growth rate of 4α-MTAPc was less than that of 4β-MTAPc prepared under identical conditions. Further, the surface coverage of the polymerized 4β-MTAPc film was greater than that of 4α-MTAPc polymerized film. Atomic force microscopy (AFM), X-ray diffraction (XRD) and UV–visible spectroscopic studies were carried out for the polymerized films of 4α-NiIITAPc (p-4α-NiIITAPc) and 4β-NiIITAPc (p-4β-NiIITAPc) alone because both Ni(II) and Co(II) polymerized films show similar trend in electropolymerization and surface coverage values. AFM images show that p-4α-NiIITAPc film contains islands and the thickness of this film was nearly three times less than that of p-4β-NiIITAPc. XRD patterns for the two polymerized films reveal that p-4β-NiIITAPc film was relatively more crystalline than p-4α-NiIITAPc film. Further, the compactness of these films was scrutinized from their barrier properties toward [Fe(CN)6]3−/4− redox couple. The differences in the polymerization growth rate of 4α-MTAPc and 4β-MTAPc, and the thicknesses of the resultant polymerized films suggest that unlike 4β-MTAPc one or two amino groups might have not involved in electropolymerization in the case of 4α-MTAPc. Further, the influence of surface coverage on the electrocatalytic properties of the polymerized films was studied by taking p-4β-CoIITAPc and p-4α-CoIITAPc films as examples. The electrocatalytic oxygen reduction current was almost same at both the electrodes suggesting that only the surface species were involved in the electrocatalytic reduction of oxygen.

Mechanistic details of the membrane perforation and passive translocation of TAT peptides

The trans-activator of transcription (TAT) peptide is regarded as the “gold standard” for cell-penetrating peptides, capable of traversing a mammalian membrane passively into the cytosolic space. This characteristic has been exploited through conjugation of TAT for applications such as drug delivery. However, the process by which TAT achieves membrane penetration remains ambiguous and unresolved. Mechanistic details of TAT peptide action are revealed herein by using three complementary methods: quartz crystal microbalance with dissipation (QCM-D), scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). When combined, these three scales of measurement define that the membrane uptake of the TAT peptide is by trans-membrane insertion using a “worm-hole” pore that leads to ion permeability across the membrane layer. AFM data provided nanometre-scale visualisation of TAT punctuation using a mammalian-mimetic membrane bilayer. The TAT peptide does not show the same specificity towards a bacterial mimetic membrane and QCM-D and SECM showed that the TAT peptide demonstrates a disruptive action towards these membranes. This investigation supports the energy-independent uptake of the cationic TAT peptide and provides empirical data that clarify the mechanism by which the TAT peptide achieves its membrane activity. The novel use of these three biophysical techniques provides valuable insight into the mechanism for TAT peptide translocation, which is essential for improvements in the cellular delivery of TAT-conjugated cargoes including therapeutic agents required to target specific intracellular locations.

Experimental and numerical investigation of strain-rate dependent mechanical properties of single living cells

The objective of this project is to investigate the strain-rate dependent mechanical behaviour of single living cells using both experimental and numerical techniques. The results revealed that living cells behave as porohyperlastic materials and that both solid and fluid phases within the cells play important roles in their mechanical responses. The research reported in this thesis provides a better understanding of the mechanisms underlying the cellular responses to external mechanical loadings and of the process of mechanical signal transduction in living cells. It would help us to enhance knowledge of and insight into the role of mechanical forces in supporting tissue regeneration or degeneration.

Microscale consolidation analysis of relaxation behavior of single living chondrocytes subjected to varying strain-rates

Besides the elastic stiffness, the relaxation behavior of single living cells is also of interest of various researchers when studying cell mechanics. It is hypothesized that the relaxation response of the cells is governed by both intrinsic viscoelasticity of the solid phase and fluid-solid interactions mechanisms. There are a number of mechanical models have been developed to investigate the relaxation behavior of single cells. However, there is lack of model enable to accurately capture both of the mechanisms. Therefore, in this study, the porohyperelastic (PHE) model, which is an extension of the consolidation theory, combined with inverse Finite Element Analysis (FEA) technique was used at the first time to investigate the relaxation response of living chondrocytes. This model was also utilized to study the dependence of relaxation behavior of the cells on strain-rates. The stress-relaxation experiments under the various strain-rates were conducted with the Atomic Force Microscopy (AFM). The results have demonstrated that the PHE model could effectively capture the stress-relaxation behavior of the living chondrocytes, especially at intermediate to high strain-rates. Although this model gave some errors at lower strain-rates, its performance was acceptable. Therefore, the PHE model is properly a promising model for single cell mechanics studies. Moreover, it has been found that the hydraulic permeability of living chondrocytes reduced with decreasing of strain-rates. It might be due to the intracellular fluid volume fraction and the fluid pore pressure gradients of chondrocytes were higher when higher strain-rates applied.

Lactose surface modification by decantation: Are drug-fine lactose ratios the key to better dispersion of salmeterol xinafoate from lactose-interactive mixtures?

Purpose The role of fine lactose in the dispersion of salmeterol xinafoate (SX) from lactose mixtures was studied by modifying the fine lactose concentration on the surface of the lactose carriers using wet decantation. Methods Fine lactose was removed from lactose carriers by wet decantation using ethanol saturated with lactose. Particle sizing was achieved by laser diffraction. Fine particle fractions (FPFs) were determined by Twin Stage Impinger using a 2.5% SX mixture, and SX was analyzed by a validated high-performance liquid chromatography method. Adhesion forces between probes of SX and silica and the lactose surfaces were determined by atomic force microscopy. Results FPFs of SX were related to fine lactose concentration in the mixture for inhalation grade lactose samples. Reductions in FPF (2-4-fold) of Aeroflo 95 and 65 were observed after removing fine lactose by wet decantation; FPFs reverted to original values after addition of micronized lactose to decanted mixtures. FPFs of SX of sieved and decanted fractions of Aeroflo carriers were significantly different (p < 0.001). The relationship between FPF and fine lactose concentration was linear. Decanted lactose demonstrated surface modification through increased SX-lactose adhesion forces; however, any surface modification other than removal of fine lactose only slightly influenced FPF. Conclusions Fine lactose played a key and dominating role in controlling FPF. SX to fine lactose ratios influenced dispersion of SX with maximum dispersion occurring as the ratio approached unity.

Photochemical design of stimuli-responsive nanoparticles prepared by supramolecular host–guest chemistry

We introduce the design of a thermoresponsive nanoparticle via sacrificial micelle formation based on supramolecular host–guest chemistry. Reversible addition–fragmentation chain transfer (RAFT) polymerization was employed to synthesize well-defined polymer blocks of poly(N,N-dimethylacrylamide) (poly(DMAAm)) (Mn,SEC = 10 700 g mol–1, Đ = 1.3) and poly(N-isopropylacrylamide) (poly(NiPAAm)) (Mn,SEC = 39 700 g mol–1, Đ = 1.2), carrying supramolecular recognition units at the chain termini. Further, 2-methoxy-6-methylbenzaldehyde moieties (photoenols, PE) were statistically incorporated into the backbone of the poly(NiPAAm) block as photoactive cross-linking units. Host–guest interactions of adamantane (Ada) (at the terminus of the poly(NiPAAm/PE) chain) and β-cyclodextrin (CD) (attached to the poly(DMAAm chain end) result in a supramolecular diblock copolymer. In aqueous solution, the diblock copolymer undergoes micellization when heated above the lower critical solution temperature (LCST) of the thermoresponsive poly(NiPAAm/PE) chain, forming the core of the micelle. Via the addition of a 4-arm maleimide cross-linker and irradiation with UV light, the micelle is cross-linked in its core via the photoinduced Diels–Alder reaction of maleimide and PE units. The adamantyl–cyclodextrin linkage is subsequently cleaved by the destruction of the β-CD, affording narrowly distributed thermoresponsive nanoparticles with a trigger temperature close to 30 °C. Polymer chain analysis was performed via size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and dynamic light scattering (DLS). The size and thermoresponsive behavior of the micelles and nanoparticles were investigated via DLS as well as atomic force microscopy (AFM).