Design of Biopolymer-Based Interstitial Therapies for the Treatment of Glioblastoma

Glioblastoma multiforme (GBM) is the most common form of primary brain cancer and has the highest morbidity rate and current treatments result in a bleak 5-year survival rate of 5.6%. Interstitial therapy is one option to increase survival. Drug delivery by interstitial therapy most commonly makes use of a polymer implant encapsulating a drug which releases as the polymer degrades. Interstitial therapy has been extensively studied as a treatment option for GBM as it provides several advantages over systemic administration of chemotherapeutics. Primarily, it can be applied behind the blood–brain barrier, increasing the number of possible chemotherapeutic candidates that can be used and reducing systemic levels of the therapy while concentrating it near the cancer source. With interstitial therapy, multiple drugs can be released locally into the brain at the site of resection as the polymer of the implant degrades, and the release profile of these drugs can be tailored to optimize combination therapy or maintain synergistic ratios. This can bypass the blood–brain barrier, alleviate systemic toxicity, and resolve drug resistance in the tumor. However, tailoring drug release requires appropriate consideration of the complex relationship between the drug, polymer, and formulation method. Drug physicochemical properties can result in intermolecular bonding with the polymeric matrix and affect drug distribution in the implant depending on the formulation method used. This review is focused on current works that have applied interstitial therapy towards GBM, discusses polymer and formulation methods, and provides design considerations for future implantable biodegradable materials.

Solvophobicity-directed assembly of microporous molecular crystals

Dense packing is a universal tendency of organic molecules in the solid state. Typical porous crystals utilize reticular strong intermolecular bonding networks to overcome this principle. Here, we report a solvophobicity-based methodology for assembling discrete molecules into a porous form and succeed in synthesizing isostructural porous polymorphs of an amphiphilic aromatic molecule Py6Mes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling Py6Mes into a columnar stacking while the columns are sterically salient and form nanopores between them. The porous packing is facilitated particularly in solvents with weak dispersion interaction due to the solvophobic effect. Conversely, solvents with strong dispersion interaction intercalate between Py6Mes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of Py6Mes-analogues, m-Py6Mes and Ph6Mes.

Anisotropic thermal expansion of the acetylene–ammonia co-crystal under Titan's conditions

Acetylene and ammonia are known to form a stable orthorhombic co-crystal under the surface conditions of Saturn's moon Titan (1.5 bar = 150 kPa, 94 K). Such a material represents a potential new class of organic minerals that could play an important role in Titan's geology. In this work, the thermal expansion of this co-crystalline system has been derived from in situ powder X-ray diffraction data obtained between 85 and 120 K. The results indicate significant anisotropy, with the majority of the expansion occurring along the c axis (∼2% over the temperature range of interest). Rietveld refinements reveal little change to the structure compared with that previously reported by Boese, Bläser & Jansen [J. Am. Chem. Soc. (2009), 131, 2104–2106]. The expansion is consistent with the alignment of C—H...N interactions along the chains in the a and b axes, and weak intermolecular bonding in the structural layers along the c axis.

A detailed look at the bonding interactions in the microsolvation of monoatomic cations

Global and local descriptors of the properties of intermolecular bonding afford a highly complex picture of the bonding interactions responsible for microsolvation of monoatomic cations.

Studies of the Cationic Polyacrylamide Adsorption on the Montmorillonite Surface in the Presence of Lead(II) Ions

The phenomena of stabilization and flocculation through the addition of polymer is widely used in many branches of industry, e.g., agriculture. Due to the high strength of intermolecular bonding, the polymers are used as an additive to control the process of soil erosion. Flocculants strengthen the soil cohesion, which limits the transport of sediments and thus the process of soil structure degradation. Also, the presence of polymers affects the increase of water infiltration into the soil and dissolved substances, including toxic compounds. Therefore, the presence of soil flocculants may influence the occurrence of heavy metal accumulation. The aim of the study was to investigate the influence of the presence of cationic polyacrylamide on lead(II) ion adsorption onto the surface of montmorillonite. The effect of cationic group content in the polymeric macromolecules, the addition order of individual adsorbates, and the lead(II) ion concentration were also determined.

Molecular Structures Polymorphism the Role of F…F Interactions in Crystal Packing of Fluorinated Tosylates

The peculiarities of interatomic interactions formed by fluorine atoms were studied in four tosylate derivatives p-CH3C6H4OSO2CH2CF2CF3 and p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5, 7) using X-ray diffraction and quantum chemical calculations. Compounds p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) were crystallized in several polymorph modifications. Analysis of intermolecular bonding was carried out using QTAIM approach and energy partitioning. All compounds are characterized by crystal packing of similar type and the contribution of intermolecular interactions formed by fluorine atoms to lattice energy is raised along with the increase of their amount. The energy of intra- and intermolecular F…F interactions is varied in range 0.5–13.0 kJ/mol. Total contribution of F…F interactions to lattice energy does not exceed 40%. Crystal structures of studied compounds are stabilized mainly by C-H…O and C-H…F weak hydrogen bonds. The analysis of intermolecular interactions and lattice energies in polymorphs of p-CH3C6H4OSO2CH2(CF2)nCHF2 (n = 1, 5) has shown that most stabilized are characterized by the least contribution of F…F interactions.

Interfibril hydrogen bonding improves the strain-rate response of natural armour

Fish scales are laminated composites that consist of plies of unidirectional collagen fibrils with twisted-plywood stacking arrangement. Owing to their composition, the toughness of scales is dependent on the intermolecular bonding within and between the collagen fibrils. Adjusting the extent of this bonding with an appropriate stimulus has implications for the design of next-generation bioinspired flexible armours. In this investigation, scales were exposed to environments of water or a polar solvent (i.e. ethanol) to influence the extent of intermolecular bonding, and their mechanical behaviour was evaluated in uniaxial tension and transverse puncture. Results showed that the resistance to failure of the scales increased with loading rate in both tension and puncture and that the polar solvent treatment increased both the strength and toughness through interpeptide bonding; the largest increase occurred in the puncture resistance of scales from the tail region (a factor of nearly 7×). The increase in strength and damage tolerance with stronger intermolecular bonding is uncommon for structural materials and is a unique characteristic of the low mineral content. Scales from regions of the body with higher mineral content underwent less strengthening, which is most likely the result of interference posed by the mineral crystals to intermolecular bonding. Overall, the results showed that flexible bioinspired composite materials for puncture resistance should enrol constituents and complementary processing that capitalize on interfibril bonds.