Ionic discotic liquid crystals: synthesis and characterization of pyridinium bromides containing a triphenylene core

Five novel pyridinium salts tethered with hexaalkoxytriphenylene molecules were synthesized by the quaternization of pyridine with ω-bromo-substituted triphenylene derivatives. Their chemical structures were determined by ¹H NMR, ¹³C NMR, IR, UV spectroscopy and elemental analysis. The thermotropic liquid crystalline properties of these salts were investigated by polarizing optical microscopy and differential scanning calorimetry. These triphenylene-based pyridinium salts with bromide as counterion were found to be mesomorphic over a wide temperature range.     

Deciphering Internal and External π-Conjugation in C3-Symmetric Multiple Azobenzene Connected Systems in Self-Assembly

Two tripodal C₃-symmetric photoswitchable molecular systems T1 and T2 are reported that have extended conjugation at external and internal positions using an acryl group. The influence of the extended π-bonds in their absorption properties, thermal relaxation of the photoisomers and their propensities in forming supramolecular self-assemblies have been explored through spectroscopy, and microscopic studies. In particular, the investigations on the self-assembly have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM), polarized optical microscopy (POM), X-ray diffraction studies (XRD) and atomic force microscopy (AFM). Remarkably, the position of the acryl group influences the behaviour of the two target molecules in supramolecular assembly, and also in the formation of photoresponsive organic hydrogels or microcrystals.     

Transition-Metal-Free Heterocyclic Carbon-Boron Bond Formation

Heteroaryl boronic acids and esters are extremely important and valuable intermediates because of their wide application in the synthesis of marketed drugs and bioactive compounds. Over the last couple of decades, the construction of highly important heteroaryl carbon-boron bonds has created huge attention. The transition-metal-free protocols are more green, less sensitive to air and moisture, and also economically advantageous over the transition-metal-based protocols. The transition-metal-free C−H borylation of heteroarenes and C−X (X=halogen) borylation of heteroaryl halides represents an excellent approach for their synthesis. Also, various cyclization and alkyne activation protocols have been recently established for their synthesis. The goal of this review article is to summarize the existing literature and the current state of the art for transition-metal-free synthesis of heteroaryl boronic acid and esters.     

Sorptive elimination of fluoride from contaminated groundwater in a fixed bed column: A kinetic model validation based study

The current investigation involves a continuous adsorption experiment in a packed bed column for the sorptive elucidation of fluoride from contaminated groundwater using an activated soil-clay mixture. Through the combination of naturally accessible laterite soil with silica enriched clay (3:1 ratio), a low-cost Al–Si heterogeneous material has been developed. Following detailed characterization, the developed materials were employed in a long-time column process to achieve a high degree of fluoride separation from real-world groundwater. In a packed bed column investigation, the effect of bed height, initial fluoride concentration, and flow rate on the breakthrough properties of the adsorption system were investigated. By using a non-linear regression equation, three model kinetics, such as the Thomas Model, Adams-Bohart Model, and Yoon-Nelson Model, were fitted to validate the column-based experimental data, by analysing the breakthrough curves profiles, and distinct kinetic parameters. The Bed Depth Service Time Analysis (BDST) model was tested to express the effect of bed height on breakthrough curves, as well as to predict the time for breakthrough, and material depletion under optimal conditions. The Thomas and Yoon-Nelson models were identified to be the most appropriate ones for describing the entire breakthrough curve, whereas the Adams-Bohart model was only utilised to predict the first half of the dynamic process. With correlation coefficients (R²) 0.96, the experimental results were well suited to Thomas, Yoon-Nelson, and Adams-Bohart models. Finally, regeneration assessment was carried out where even after four cycles of operation, regenerated adsorbent showed a rejection efficacy of 78% to fluoride that proves the viability of the material and methodology.     

Dosimetric gelator probes and their application as sensors

Supramolecular gels formed by the self-assembly of organic molecules are useful in many areas from materials to medicine. Of the different applications, exploitation of gels for the visual detection of analytes is a fairly recent trend in gel chemistry. Most of the gel-based sensors rely on non-covalent interactions between the gelator molecules and the added chemical analytes and therefore, often suffer from less selectivity and long response time. In this context, dosimetric gelator probes are superior to other gel-based sensors with high selectivity and fast response time. Unlike non-covalent binding sites, dosimetric gelators typically contain a reaction centre and undergo a specific chemical reaction selective to an analyte resulting in either formation or rupturing of covalent bonds. In this review, we provide an up-to-date report of various reaction-based gel systems applied for the sensing of analytes. We elaborately discuss the concept, design principles, self-assembly properties, and reaction mechanisms of such gelators. We also highlight the limitations, challenges, and the necessity of further exploration of dosimetric gels in this domain.     

Coordination-based self-assembled capsules (SACs) for protein,CRISPR–Cas9, DNA and RNA delivery

Biologics, such as functional proteins and nucleic acids, have recently dominated the drug market and comprise seven out of the top 10 best-selling drugs. Biologics are usually polar, heat sensitive, membrane impermeable and subject to enzymatic degradation and thus require systemic routes of administration and delivery. Coordination-based delivery vehicles, which include nanosized extended metal–organic frameworks (nMOFs) and discrete coordination cages, have gained a lot of attention because of their remarkable biocompatibility, in vivo stability, on-demand biodegradability, high encapsulation efficiency, easy surface modification and moderate synthetic conditions. Consequently, these systems have been extensively utilized as carriers of biomacromolecules for biomedical applications. This review summarizes the recent applications of nMOFs and coordination cages for protein, CRISPR–Cas9, DNA and RNA delivery. We also highlight the progress and challenges of coordination-based platforms as a promising approach towards clinical biomacromolecule delivery and discuss integral future research directions and applications.

SACs can be efficiently used to load biologics such as proteins, CRISPR–Cas9, DNA and RNA and release them on-demand.     

Dynamic Hydrogen-Bonded Zinc Adeninate Framework (ZAF) for Immobilization of Catalytic DNA

Effective immobilization and delivery of genetic materials is at the forefront of biological and medical research directed toward tackling scientific challenges such as gene therapy and cancer treatment. Herein we present a biologically inspired hydrogen-bonded zinc adeninate framework (ZAF) consisting of zinc adeninate macrocycles that self-assemble into a 3D framework through adenine-adenine interactions. ZAF can efficiently immobilize DNAzyme with full protection against enzyme degradation and physiological conditions until it is successfully delivered into the nucleus. As compared to zeolitic imidazolate frameworks (ZIFs), ZAFs are twofold more biocompatible with a significant loading efficiency of 96 %. Overall, our design paves the way for expanding functional hydrogen-bonding-based systems as potential platforms for the loading and delivery of biologics.     

Maximal Contractive Tuples

Maximality of a contractive tuple of operators is considered. A characterization for a contractive tuple to be maximal is obtained. The notion of maximality for a submodule of the Drury–Arveson module on the \(d\) -dimensional unit ball \({\mathbb {B}}_d\) is defined. For \(d=1\) , it is shown that every submodule of the Hardy module over the unit disc is maximal. But for \(d\ge 2\) we prove that any homogeneous submodule or submodule generated by polynomials is not maximal. A characterization of maximal submodules is obtained.     

Vanishing Derivations and Co-Centralizing Generalized Derivations on Multilinear Polynomials in Prime Rings

Let R be a noncommutative prime ring of characteristic different from 2 with Utumi quotient ring U and extended centroid C, and f(x₁,…, x_n) be a multilinear polynomial over C, which is not central valued on R. Suppose that F and G are two generalized derivations of R and d is a nonzero derivation of R such that d(F(f(r))f(r) ? f(r)G(f(r))) = 0 for all r = (r₁,…, r_n) ∈ Rⁿ, then one of the following holds:

1. There exist a, p, q, c ∈ U and λ ∈C such that F(x) = ax + xp + λx, G(x) = px + xq and d(x) = [c, x] for all x ∈ R, with [c, a ? q] = 0 and f(x₁,…, x_n)² is central valued on R;

2. There exists a ∈ U such that F(x) = xa and G(x) = ax for all x ∈ R;

3. There exist a, b, c ∈ U and λ ∈C such that F(x) = λx + xa ? bx, G(x) = ax + xb and d(x) = [c, x] for all x ∈ R, with b + αc ∈ C for some α ∈C;

4. R satisfies s₄ and there exist a, b ∈ U and λ ∈C such that F(x) = λx + xa ? bx and G(x) = ax + xb for all x ∈ R;

5. There exist a′, b, c ∈ U and δ a derivation of R such that F(x) = a′x + xb ? δ(x), G(x) = bx + δ(x) and d(x) = [c, x] for all x ∈ R, with [c, a′] = 0 and f(x₁,…, x_n)² is central valued on R.

     

Restricting statistical convergence

We first introduce a new notion called statistical convergence of order α and primarily show that it gives rise to a decreasing chain of closed linear subspaces of the space of all bounded real sequences with sup norm which never coincides with the class of convergent sequences and in fact their intersection properly contains the class of convergent sequences. We then show that the same method can be applied for double sequences also and introduce the notion of statistical convergence of order (α,β).