Versatile and Accessible Magnetic Diagnosis Platform with Different Types of Magnetic Particles for Liquid and Solid Biopsies.

The diagnosis of liquid and solid biopsies by different instruments makes the clinic loading difficult in many aspects. Given the compositions of magnetic particles (MPs) with diverse characterizations and the innovative acoustic type of vibration sample magnetometer (VSM), the versatile, accessible magnetic diagnosis platform was proposed to meet clinical demands, such as low loading for multiple biopsies. In liquid biopsies of alpha-fetoprotein (AFP) standard solutions and subject serums, molecular concentration was analyzed from saturation magnetization by the soft type of Fe3O4 MPs with AFP bioprobe coating. In the phantom mixture simulated as bounded MPs in tissue, the bounded MPs was evaluated from the area of the hysteresis loop by hard type of cobalt MPs without bio-probes coating. Not only a calibration curve was founded for many hepatic cell carcinoma stages, but also microscale images verified the Ms increase due to magnetic protein clusters, etc. Hence, its wide populations in clinics could be expected.

Magnetic Clustering Effect during the Association of Biofunctionalized Magnetic Nanoparticles with Biomarkers.

We report herein an investigation into dynamic magnetic clustering that occurs during immunoassays as biofunctionalized magnetic nanoparticles (BMNs) become associated with biotargets. We measure the dynamic effective relaxation time τeff(t) and use scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to investigate the C-reactive protein (CRP) as it associates with the BMN Fe3O4-antiCRP to form the magnetic cluster Fe3O4-antiCRP-CRP. The results indicate that τeff(t) increases with increasing association time. In addition, the ration Δτeff/τ0 as a function of CRP concentration follows a characteristic logistic function, which provides a basis for estimating the quantity of biomolecules with a detection sensitivity close to 0.1 ppm. After the association, SEM and TEM images show that CRP and Fe3O4-antiCRP conjugate to form Fe3O4-antiCRP-CRP clusters hundreds of nanometers in size. The SEM and TEM images provide direct evidence of the formation of magnetic clustering.

Gelation of a solution of poly(3-hexylthiophene) greatly retards its crystallization rate in the subsequently cast film.

We compared the crystallization rate of poly(3-hexylthiophene) (P3HT) in the film cast from the gel (called "gel-cast film") with that in the film cast from the liquid solution (called "solution-cast film") to understand the effect of solution structure on the structural development in the subsequently cast film of conjugated polymer. P3HT was found to form a homogeneous liquid solution with xylene at elevated temperature. When the freshly prepared semidilute solution was allowed to age at room temperature, the solution transformed into a gel in which a significant amount of nanowhiskers formed. The nanowhiskers in the gel were effectively transferred to the corresponding cast film, while the film cast from the freshly prepared solution only contained a small amount of such a morphological entity. The in situ small-angle X-ray scattering (SAXS) measurement and thermal analysis revealed that both the cold and melt crystallization of P3HT in the gel-cast film were much slower than those in the solution-cast counterpart. The retardation of crystallization rate in the gel-cast film was attributed to the abundance of the nanowhiskers. In this case, the crystallization of P3HT occurred predominantly within the individual nanowhiskers and the mesh regions in the networks of the whiskers, where their limited sizes in at least one dimension imposed a strong spatial constraint to the crystal growth and chain motion for crystallization.

Gelation behavior of poly(9,9-dioctylfluorene)/poly[9,9-di(2-ethylhexyl)-fluorenyl-2,7-diyl] blend in methylcyclohexane solutions.

We investigated the gelation behavior of the blend of two light-emitting polyfluorenes, i.e., poly(9,9-dioctylfluorene-2,7-diyl) (PF(8)) and poly[9,9-di(2-ethylhexyl)-fluorenyl-2,7-diyl] (PF(2/6)), in solutions with methylcyclohexane (MCH). Upon prolonged aging at room temperature, dynamic light scattering revealed that phase separation in the initially well-mixed solutions occurred via spinodal decomposition, yielding a PF(8)/PF(2/6)-enriched phase and an isotropic solvent-rich phase. Sheetlike aggregates in which a portion of the PF(8) chains adopted the ß conformation were formed in the polymer-enriched phase, as revealed by small-angle X-ray scattering and optical spectroscopy. Macroscopically, the phase separation transformed the original viscous liquid solution into a gel. Measurements of the gelation temperature (T(gel)), gel-to-sol transition temperature (T(g-s)), and spinodal decomposition temperature (T(SD)) indicated that gelation (and hence phase separation) became more difficult with increasing content of PF(2/6). The presence of PF(2/6) also hindered formation of the ß-phase of PF(8.) Therefore, the microstructure and photophysical properties of PF(8)/PF(2/6) in MCH solution can be tuned by the composition of the two polymers.

A dual-emission Förster resonance energy transfer nanoprobe for sensing/imaging pH changes in the biological environment.

A dual-emission nanoprobe that can sense changes in the environmental pH is designed based on the concept of pH-responsive Förster resonance energy transfer induced by the conformational transition of an associating polyelectrolyte, N-palmitoyl chitosan, bearing a donor (Cy3) or an acceptor (Cy5) moiety. We demonstrate that the developed pH-responsive nanoprobe can be used to ratiometrically image and thus discriminate the pH changes in the biological environment at different length scales.

Scattering study of the conformational structure and aggregation behavior of a conjugated polymer solution.

The conformational structure and the interchain aggregation behavior of a semirigid conjugated polymer bearing a decyl side chain, poly(2,3-diphenyl-5-decyl-1,4-phenylenevinylene) (DP10-PPV), in solutions with chloroform and toluene have been investigated by means of small-angle neutron scattering (SANS), static light scattering (SLS) and dynamic light scattering (DLS). The radius of gyration, persistence length, and the second virial coefficient of the polymer in dilute solution as determined by SLS were higher in chloroform than in toluene; consequently, the polymer assumed a more extended wormlike chain conformation in the former. The difference in the strength of interaction in the two solvents gave rise to contrasting aggregation behavior of the polymer in the semidilute regime. While only a minor fraction of the polymer underwent segmental association in chloroform, a considerable fraction of it formed clusters (microgels) with several micrometers in size in toluene. These clusters were further found to consist of sheetlike nanodomains. Compared with the DP-PPV bearing a shorter hexyl side chain, DP6-PPV, the aggregates of DP10-PPV in toluene were weaker as they could be easily disrupted by moderate heating. This was attributed to a lack of strong pi-pi interaction between the DP10-PPV segments due to the greater steric hindrance imposed by the longer decyl side chains.

Aggregation of conjugated polymers in aromatic solvent.

Segments of conjugated polymers display the propensity to aggregate in solutions with common organic solvents. Here we revealed that the segmental aggregation of a conjugated polymer, poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl), (PF2/6), in toluene was stabilized by the polymer-solvent complex formation through pi-pi stacking induction of solvent molecules and polymer segments. In this case, a portion of the solvent was trapped inside the aggregate domains upon bringing the system to the subambient temperatures. The residence time of these associated solvent molecules became long enough to yield a separate upfield-shifted NMR resonance. The line-shape of this resonance revealed alignment of the polymer segments in the aggregates. A portion of the solvent was frozen in the compact structure due to the formation of strong polymer-solvent complex.

Fractal aggregates of conjugated polymer in solution state.

Semirigid conjugated polymers have received much scientific and technological interest due to their unique electrical and photonic semiconducting properties. Spectroscopic studies have indicated that these polymers underwent interchain aggregation in the solution state even at large dilution; however, the origin of this event and the structure of the resultant aggregates remained the crucial issues to be resolved. In the present study, we revealed that the interchain aggregation of a conjugated polymer, poly(2,3-diphenyl-5-hexyl-1,4-phenylenevinylene) (DP6-PPV), in solutions with chloroform and toluene generated network aggregates with the hydrodynamic radii of several micrometers. Small angle neutron scattering (SANS) demonstrated that the internal structure of these aggregates could be characterized by the mass fractal dimensions of 2.2-2.7. The networks were looser in chloroform but became highly compact in the poorer toluene solvent due to severe segmental association. Increasing the temperature alleviated the segmental association in toluene while largely retaining the mass fractal dimension of the aggregates. However, the interchain aggregation was never completely dissipated by the heating, suggesting the existence of two types of segmental association with distinct stability. The highly stable segmental association that could neither be solvated by chloroform nor be disrupted thermally in toluene was attributed to the pi-pi complex already present in the DP6-PPV powder used for the solution preparation. The chains tied firmly by this complex formed network aggregates in the solution and hence reduced the entropy of mixing of the polymer. In the poorer toluene solvent, further segmental association took place within the preexisting aggregates, making the networks more compact. This type of segmental association could be disrupted by moderate heating, and its occurrence was ascribed to the poor affinity of the aliphatic side chains of DP6-PPV for toluene.