Does thermotropic liquid crystalline self-assembly control biological activity in amphiphilic amino acids? - tyrosine ILCs as a case study.

Amphiphilic amino acids represent promising scaffolds for biologically active soft matter. In order to understand the bulk self-assembly of amphiphilic amino acids into thermotropic liquid crystalline phases and their biological properties a series of tyrosine ionic liquid crystals (ILCs) was synthesized, carrying a benzoate unit with 0-3 alkoxy chains at the tyrosine unit and a cationic guanidinium head group. Investigation of the mesomorphic properties by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (WAXS, SAXS) revealed smectic A bilayers (SmAd) for ILCs with 4-alkoxy- and 3,4-dialkoxybenzoates, whereas ILCs with 3,4,5-trisalkoxybenzoates showed hexagonal columnar mesophases (Colh), while different counterions had only a minor influence. Dielectric measurements revealed a slightly higher dipole moment of non-mesomorphic tyrosine-benzoates as compared to their mesomorphic counterparts. The absence of lipophilic side chains on the benzoate unit was important for the biological activity. Thus, non-mesomorphic tyrosine benzoates and crown ether benzoates devoid of additional side chains at the benzoate unit displayed the highest cytotoxicities (against L929 mouse fibroblast cell line) and antimicrobial activity (against Escherichia coli ΔTolC and Staphylococcus aureus) and promising selectivity ratio in favour of antimicrobial activity.

Tailoring liquid crystalline self-assembly and de Vries behavior of azulenes via lateral and core substitution.

The azulene moiety is a highly attractive building block in optoelectronic applications due to its unique properties. For high-performing devices, the molecular orientation is crucial and can be controlled through liquid-crystalline self-assembly. Recent work showed that liquid crystalline derivatives bearing the 2-phenyl-azulene-1-nitrile core formed broad de Vries-type SmA and SmC phases. For exact understanding of the structure-property relationship, a series of 2-(hetero)aryl-azulenes has been synthesized varying the chain linkage, the lateral substituent, and the aromatic ring. Small changes of the molecular structure determined whether the orthogonal SmA phase or the tilted SmC phase is predominant. Implementation of alkyne chains instead of alkoxy chains resulted in the reduction of phase transition temperatures and formation of mesophases at room temperature. Furthermore, de Vries-like behavior was investigated and reduction values between R = 0.35 and 0.74 were measured which supported the hypothesis that in this system de Vries-like behavior is caused by steric repulsion of the lateral substituent. The control of the phase geometry by the molecular structure might be used for improved molecular orientation in optoelectronic materials.

Liquid crystalline self-assembly of azulene-thiophene hybrids and their applications as OFET materials.

Orientational control within thin films is crucial for the preparation of organic field effect transistors (OFETs). The highly ordered liquid crystalline smectic E phase (SmE) is known as a powerful template for solution processed thin films. Here, we describe the synthesis and characterization of three novel azulene-thiophene hybrid materials. Liquid crystalline characterization showed the presence of wide SmE phases. Thin films were prepared by spin-coating at mesophase temperature. Due to the self-aligning properties of the SmE phase uniformly flat films with good molecular alignment were manufactured. Top contact bottom gate OFETs showed mobilities up to (3.3 ± 0.5) × 10-3 cm2 V-1 s-1.

The Role of 3D Printing in Planning Complex Medical Procedures and Training of Medical Professionals-Cross-Sectional Multispecialty Review.

Medicine is a rapidly-evolving discipline, with progress picking up pace with each passing decade. This constant evolution results in the introduction of new tools and methods, which in turn occasionally leads to paradigm shifts across the affected medical fields. The following review attempts to showcase how 3D printing has begun to reshape and improve processes across various medical specialties and where it has the potential to make a significant impact. The current state-of-the-art, as well as real-life clinical applications of 3D printing, are reflected in the perspectives of specialists practicing in the selected disciplines, with a focus on pre-procedural planning, simulation (rehearsal) of non-routine procedures, and on medical education and training. A review of the latest multidisciplinary literature on the subject offers a general summary of the advances enabled by 3D printing. Numerous advantages and applications were found, such as gaining better insight into patient-specific anatomy, better pre-operative planning, mock simulated surgeries, simulation-based training and education, development of surgical guides and other tools, patient-specific implants, bioprinted organs or structures, and counseling of patients. It was evident that pre-procedural planning and rehearsing of unusual or difficult procedures and training of medical professionals in these procedures are extremely useful and transformative.

Self-Assembly of Aminocyclopropenium Salts: En†Route to Deltic Ionic Liquid Crystals.

Aminocyclopropenium ions have raised much attention as organocatalysts and redox active polymers. However, the self-assembly of amphiphilic aminocyclopropenium ions remains challenging. The first deltic ionic liquid crystals based on aminocyclopropenium ions have been developed. Differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction provided insight into the unique self-assembly and nanosegregation of these liquid crystals. While the combination of small headgroups with linear p-alkoxyphenyl units led to bilayer-type smectic mesophases, wedge-shaped units resulted in columnar mesophases. Upon increasing the size and polyphilicity of the aminocyclopropenium headgroup, a lamellar phase was formed.