Macromolecular brushes with a gradient of side-chain spacing along the backbone have been synthesized by the "grafting from" approach using atom transfer radical polymerization. A macroinitiator was prepared in two steps, first by conducting a gradient copolymerization of MMA and HEMA-TMS followed by transformation of the resulting poly(MMA-grad-HEMA-TMS) to poly(MMAgrad-BPEM). The gradient composition of the macroinitiator was a forced gradient formed by continuous feeding of HEMA-TMS during MMA polymerization. The gradient structure was characterized by monitoring monomer conversion (GC) and molecular weight evolution (GPC) during copolymerization. AFM measurements demonstrated the characteristic anisotropy of the molecular structure by resolving individual brush molecules with a bulky head and a thin tail.

This Article investigates different types of networks formed from tilapia fish gelatin (10% w/w) in the presence and absence of the enzymatic cross-linker microbial transglutaminase. The influence of the temperature protocol and cross-linker concentration (0-55 U mTGase/g gelatin) was examined in physical, chemical, and hybrid gels, where physical gels arise from the formation of triple helices that act as junction points when the gels are cooled below the gelation point. A combination of rheology and optical rotation was used to study the evolution of the storage modulus (G') over time and the number of triple helices formed for each type of gel. We attempted to separate the final storage modulus of the gels into its chemical and physical contributions to examine the existence or otherwise of synergism between the two types of networks. Our experiments show that the gel characteristics vary widely with the thermal protocol. The final storage modulus in chemical gels increased with enzyme concentration, possibly due to the preferential formation of closed loops at low cross-linker amount. In chemical-physical gels, where the physical network (helices) was formed consecutively to the covalent one, we found that below a critical enzyme concentration the more extensive the chemical network is (as measured by G'), the weaker the final gel is. The storage modulus attributed to the physical network decreased exponentially as a function of G' from the chemical network, but both networks were found to be purely additive. Helices were not thermally stabilized. The simultaneous formation of physical and chemical networks (physical-co-chemical) resulted in G' values higher than the individual networks formed under the same conditions. Two regimes were distinguished: at low enzyme concentration (10-20 U mTGase/g gelatin), the networks were formed in series, but the storage modulus from the chemical network was higher in the presence of helices (compared to pure chemical gels); at higher enzyme concentration (30-40 U mTGase/g gelatin), strong synergistic effects were found as a large part of the covalent network became ineffective upon melting of the helices.

Absolute-molecular-weight distribution of cylindrical brush molecules were determined using a combination of the Langmuir Blodget (LB) technique and Atomic Force Microscopy (AFM). The LB technique gives mass density of a monolayer, i.e., mass per unit area, whereas visualization of individual molecules by AFM enables accurate measurements of the molecular density, i.e., number of molecules per unit area. From the ratio of the mass density to the molecular density, one can determine the absolute value for the number average molecular weight. Assuming that the structure of brush molecules is uniform along the backbone, the length distribution should be virtually identical to the molecular weight distribution. Although we used only brush molecules for demonstration purpose, this approach can be applied for a large variety of molecular and colloidal species that can be visualized by a microscopic technique.

Charge distribution in insulators has received considerable attention but still poses great scientific challenges, largely due to a current lack of firm knowledge about the nature and speciation of charges. Recent studies using analytical microscopies have shown that insulators contain domains with excess fixed ions forming various kinds of potential distribution patterns, which are also imaged by potential mapping using scanning electric probe microscopy. Results from the authors' laboratory show that solid insulators are seldom electroneutral, as opposed to a widespread current assumption. Excess charges can derive from a host of charging mechanisms: excess local ion concentration, radiochemical and tribochemical reactions added to the partition of hydroxonium and hydronium ions derived from atmospheric water. The last factor has been largely overlooked in the literature, but recent experimental evidence suggests that it plays a decisive role in insulator charging. Progress along this line is expected to help solve problems related to unwanted electrostatic discharges, while creating new possibilities for energy storage and handling as well as new electrostatic devices.

The structure of dispersions of TEMPO-oxidised cellulose nanofibrils (OCNF), at various concentrations, in water and in NaCl aqueous solutions, was probed using small angle X-ray scattering (SAXS). OCNF are modelled as rod-like particles with an elliptical cross-section of 10 nm and a length greater than 100 nm. As OCNF concentration increases above 1.5 wt%, repulsive interactions between fibrils are evidenced, modelled by the interaction parameter νRPA > 0. This corresponds to gel-like behaviour, where G' > G'' and the storage modulus, G', shows weak frequency dependence. Hydrogels can also be formed at OCNF concentration of 1 wt% in 0.1 M NaCl(aq). SAXS patterns shows an increase of the intensity at low angle that is modelled by attractive interactions (νRPA < 0) between OCNF, arising from the screening of the surface charge of the fibrils. Results are supported by ζ potential and cryo-TEM measurements.

Polymeric micelles, in particular PEO-PPO-based Pluronic, have emerged as promising drug carriers, while cyclodextrins (CD), cyclic oligosaccharides with an apolar cavity, have long been used for their capacity to form inclusion complexes with drugs. Dimethylated β-cyclodextrin (DIMEB) has the capacity to fully breakup F127 Pluronic micelles, while this effect is substantially hindered if drugs are loaded within the micellar aggregates. Four drugs were studied at physiological temperature: lidocaine (LD), pentobarbital sodium salt (PB), sodium naproxen (NP), and sodium salicylate (SAL); higher temperatures shift the equilibrium toward higher drug partitioning and lower drug/CD binding compared to 25 °C ( Valero, M.; Dreiss, C. A. Growth, Shrinking, and Breaking of Pluronic Micelles in the Presence of Drugs and/or β-Cyclodextrin, a Study by Small-Angle Neutron Scattering and Fluorescence Spectroscopy . Langmuir 2010 , 26 , 10561 - 10571 ). The impact of drugs on micellar structure was characterized by small-angle neutron scattering (SANS), while their solubilization locus was revealed by 2D NOESY NMR. UV and fluorescence spectroscopy, Dynamic and Static Light Scattering were employed to measure a range of micellar properties and drug:CD interactions: binding constant, drug partitioning within the micelles, critical micellar concentration of the loaded micelles, aggregation number (N). Critically, time-resolved SANS (TR-SANS) reveal that micellar breakup in the presence of drugs is substantially slower (100s of seconds) than for the free micelles (<100 ms) ( Valero, M.; Grillo, I.; Dreiss, C. A. Rupture of Pluronic Micelles by Di-Methylated β-Cyclodextrin Is Not Due to Polypseudorotaxane Formation . J. Phys. Chem. B 2012 , 116 , 1273 - 1281 ). These results combined together give new insights into the mechanisms of protection of the drugs against CD-induced micellar breakup. The outcomes are practical guidelines to improve the design of drug delivery systems as well as a better understanding of competitive assembly mechanisms leading to shape and function modulation.

The native states of proteins generally have stable well-defined folded structures endowing these biomolecules with specific functionality and molecular recognition abilities. Here we explore the potential of using folded globular polyproteins as building blocks for hydrogels. Photochemically cross-linked hydrogels were produced from polyproteins containing either five domains of I27 ((I27)5), protein L ((pL)5), or a 1:1 blend of these proteins. SAXS analysis showed that (I27)5 exists as a single rod-like structure, while (pL)5 shows signatures of self-aggregation in solution. SANS measurements showed that both polyprotein hydrogels have a similar nanoscopic structure, with protein L hydrogels being formed from smaller and more compact clusters. The polyprotein hydrogels showed small energy dissipation in a load/unload cycle, which significantly increased when the hydrogels were formed in the unfolded state. This study demonstrates the use of folded proteins as building blocks in hydrogels, and highlights the potential versatility that can be offered in tuning the mechanical, structural, and functional properties of polyproteins.

Biofuels have the potential to alter the transport and agricultural sectors of decarbonizing societies. Yet, the sustainability of these fuels has been questioned in recent years in connection with food versus fuel trade-offs, carbon accounting, and land use. Recognizing the complicated playing field for current decision-makers, we examine the technical attributes, policy, and global investment activity for biofuels (primarily liquids). Differences in feedstock and fuel types are considered, in addition to policy approaches of major producer countries. Issues with recent, policy-driven trade developments are highlighted to emphasize how systemic complexities associated with sustainability must also be managed. We conclude with near-term areas to watch.