scholarly journals Towards understanding π-stacking interactions between non-aromatic rings

IUCrJ ◽  
2019 ◽  
Vol 6 (2) ◽  
pp. 156-166 ◽  
Author(s):  
Krešimir Molčanov ◽  
Biserka Kojić-Prodić
Keyword(s):  
Crystal Engineering ◽  
Metal Chelate ◽  
Chemical Species ◽  
Functional Materials ◽  
Closed Shell ◽  
Aromatic Rings ◽  
Wide Range ◽  
Covalent Contribution ◽  
Shell Rings ◽  
Main Component

The first systematic study of π interactions between non-aromatic rings, based on the authors' own results from an experimental X-ray charge-density analysis assisted by quantum chemical calculations, is presented. The landmark (non-aromatic) examples include quinoid rings, planar radicals and metal-chelate rings. The results can be summarized as: (i) non-aromatic planar polyenic rings can be stacked, (ii) interactions are more pronounced between systems or rings with little or no π-electron delocalization (e.g. quinones) than those involving delocalized systems (e.g. aromatics), and (iii) the main component of the interaction is electrostatic/multipolar between closed-shell rings, whereas (iv) interactions between radicals involve a significant covalent contribution (multicentric bonding). Thus, stacking covers a wide range of interactions and energies, ranging from weak dispersion to unlocalized two-electron multicentric covalent bonding (`pancake bonding'), allowing a face-to-face stacking arrangement in some chemical species (quinone anions). The predominant interaction in a particular stacked system modulates the physical properties and defines a strategy for crystal engineering of functional materials.

Pharmaceutical Co-Crystals - Design, Development and Applications

2020 ◽  
Vol 10 (3) ◽  
pp. 169-184
Author(s):  
Rachna Anand ◽  
Arun Kumar ◽  
Arun Nanda
Keyword(s):  
Physicochemical Properties ◽  
Crystal Engineering ◽  
Pharmacological Action ◽  
Physicochemical Characteristics ◽  
Research Area ◽  
Dissolution Profile ◽  
Design Development ◽  
Drug Molecule ◽  
Wide Range ◽  
Major Factors

Background: Solubility and dissolution profile are the major factors which directly affect the biological activity of a drug and these factors are governed by the physicochemical properties of the drug. Crystal engineering is a newer and promising approach to improve physicochemical characteristics of a drug without any change in its pharmacological action through a selection of a wide range of easily available crystal formers. Objective: The goal of this review is to summarize the importance of crystal engineering in improving the physicochemical properties of a drug, methods of design, development, and applications of cocrystals along with future trends in research of pharmaceutical co-crystals. Co-crystallization can also be carried out for the molecules which lack ionizable functional groups, unlike salts which require ionizable groups. Conclusion: Co-crystals is an interesting and promising research area amongst pharmaceutical scientists to fine-tune the physicochemical properties of drug materials. Co-crystallization can be a tool to increase the lifecycle of an older drug molecule. Crystal engineering carries the potential of being an advantageous technique than any other approach used in the pharmaceutical industry. Crystal engineering offers a plethora of biopharmaceutical and physicochemical enhancements to a drug molecule without the need of any pharmacological change in the drug.

scholarly journals Characterizing Bacterial Cellulose Produced byKomagataeibacter sucrofermentans H-110 on Molasses Medium and Obtaining a Biocomposite Based on It for the Adsorption of Fluoride

Polymers ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1422
Author(s):  
Viktor V. Revin ◽  
Alexander V. Dolganov ◽  
Elena V. Liyaskina ◽  
Natalia B. Nazarova ◽  
Anastasia V. Balandina ◽  
...  
Keyword(s):  
Composite Material ◽  
Adsorption Capacity ◽  
Bacterial Cellulose ◽  
Functional Materials ◽  
Degree Of Crystallinity ◽  
Maximum Adsorption Capacity ◽  
Fluoride Ions ◽  
Sorption Ability ◽  
Wide Range ◽  
Biocomposite Material

Currently, there is an increased demand for biodegradable materials in society due to growing environmental problems. Special attention is paid to bacterial cellulose, which, due to its unique properties, has great prospects for obtaining functional materials for a wide range of applications, including adsorbents. In this regard, the aim of this study was to obtain a biocomposite material with adsorption properties in relation to fluoride ions based on bacterial cellulose using a highly productive strain of Komagataeibacter sucrofermentans H-110 on molasses medium. Films of bacterial cellulose were obtained. Their structure and properties were investigated by FTIR spectroscopy, NMR, atomic force microscopy, scanning electron microscopy, and X-ray structural analysis. The results show that the fiber thickness of the bacterial cellulose formed by the K. sucrofermentans H-110 strain on molasses medium was 60–90 nm. The degree of crystallinity of bacterial cellulose formed on the medium was higher than on standard Hestrin and Schramm medium and amounted to 83.02%. A new biocomposite material was obtained based on bacterial cellulose chemically immobilized on its surface using atomic-layer deposition of nanosized aluminum oxide films. The composite material has high sorption ability to remove fluoride ions from an aqueous medium. The maximum adsorption capacity of the composite is 80.1 mg/g (F/composite). The obtained composite material has the highest adsorption capacity of fluoride from water in comparison with other sorbents. The results prove the potential of bacterial cellulose-based biocomposites as highly effective sorbents for fluoride.

scholarly journals Ring-Forming Polymerization toward Perfluorocyclobutyl and Ortho-Diynylarene-Derived Materials: From Synthesis to Practical Applications

Materials ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1486
Author(s):  
Eugene B. Caldona ◽  
Ernesto I. Borrego ◽  
Ketki E. Shelar ◽  
Karl M. Mukeba ◽  
Dennis W. Smith
Keyword(s):  
Chemical Resistance ◽  
Structural Features ◽  
Review Article ◽  
Aryl Ether ◽  
Aromatic Rings ◽  
Practical Applications ◽  
Repeat Units ◽  
Wide Range ◽  
Synthetic Routes ◽  
The Cost

Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer’s performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across their backbones have generally been shown to exhibit higher optical transparency, lower water absorption, and higher glass transition temperatures. These specifically include polymers built with either substituted alicyclic structures or aromatic rings, or both. In this review article, we highlight two useful ring-forming polymer groups, perfluorocyclobutyl (PFCB) aryl ether polymers and ortho-diynylarene- (ODA) based thermosets, both demonstrating outstanding thermal stability, chemical resistance, mechanical integrity, and improved processability. Different synthetic routes (with emphasis on ring-forming polymerization) and properties for these polymers are discussed, followed by their relevant applications in a wide range of aspects.

scholarly journals Oxidative cyclo-rearrangement of helicenes into chiral nanographenes

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chengshuo Shen ◽  
Guoli Zhang ◽  
Yongle Ding ◽  
Na Yang ◽  
Fuwei Gan ◽  
...  
Keyword(s):  
Functional Materials ◽  
Optical Devices ◽  
Oxidative Cyclization ◽  
Synthetic Chemistry ◽  
Aromatic Rings ◽  
Cyclization Reactions ◽  
Rearrangement Reaction ◽  
Skeletal Reconstruction ◽  
Gradual Release

AbstractNanographenes are emerging as a distinctive class of functional materials for electronic and optical devices. It is of remarkable significance to enrich the precise synthetic chemistry for these molecules. Herein, we develop a facile strategy to recompose helicenes into chiral nanographenes through a unique oxidative cyclo-rearrangement reaction. Helicenes with 7~9 ortho-fused aromatic rings are firstly oxidized and cyclized, and subsequently rearranged into nanographenes with an unsymmetrical helicoid shape through sequential 1,2-migrations. Such skeletal reconstruction is virtually driven by the gradual release of the strain of the highly distorted helicene skeleton. Importantly, the chirality of the helicene precursor can be integrally inherited by the resulting nanographene. Thus, a series of chiral nanographenes are prepared from a variety of carbohelicenes and heterohelicenes. Moreover, such cyclo-rearrangement reaction can be sequentially or simultaneously associated with conventional oxidative cyclization reactions to ulteriorly enrich the geometry diversity of nanographenes, aiming at innovative properties.

scholarly journals Advanced Functional Materials Based on Nanocellulose for Pharmaceutical/Medical Applications

Pharmaceutics ◽  
2021 ◽  
Vol 13 (8) ◽  
pp. 1125
Author(s):  
Raluca Nicu ◽  
Florin Ciolacu ◽  
Diana E. Ciolacu
Keyword(s):  
Rapid Development ◽  
Cellulose Nanofibrils ◽  
Functional Materials ◽  
Medical Applications ◽  
Bacterial Nanocellulose ◽  
Green Materials ◽  
Wide Range ◽  
In Vivo Cytotoxicity

Nanocelluloses (NCs), with their remarkable characteristics, have proven to be one of the most promising “green” materials of our times and have received special attention from researchers in nanomaterials. A diversity of new functional materials with a wide range of biomedical applications has been designed based on the most desirable properties of NCs, such as biocompatibility, biodegradability, and their special physicochemical properties. In this context and under the pressure of rapid development of this field, it is imperative to synthesize the successes and the new requirements in a comprehensive review. The first part of this work provides a brief review of the characteristics of the NCs (cellulose nanocrystals—CNC, cellulose nanofibrils—CNF, and bacterial nanocellulose—BNC), as well as of the main functional materials based on NCs (hydrogels, nanogels, and nanocomposites). The second part presents an extensive review of research over the past five years on promising pharmaceutical and medical applications of nanocellulose-based materials, which have been discussed in three important areas: drug-delivery systems, materials for wound-healing applications, as well as tissue engineering. Finally, an in-depth assessment of the in vitro and in vivo cytotoxicity of NCs-based materials, as well as the challenges related to their biodegradability, is performed.

scholarly journals Physical Properties of Thermoplastic Starch Derived from Natural Resources and Its Blends: A Review

Polymers ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1396
Author(s):  
Z. N. Diyana ◽  
R. Jumaidin ◽  
Mohd Zulkefli Selamat ◽  
Ihwan Ghazali ◽  
Norliza Julmohammad ◽  
...  
Keyword(s):  
Thermoplastic Starch ◽  
Natural Fibre ◽  
Polymer Materials ◽  
Secondary Pollution ◽  
Wide Range ◽  
Potential Applications ◽  
Long Time ◽  
To Come ◽  
Main Component ◽  
Significant Attention

Thermoplastic starch composites have attracted significant attention due to the rise of environmental pollutions induced by the use of synthetic petroleum-based polymer materials. The degradation of traditional plastics requires an unusually long time, which may lead to high cost and secondary pollution. To solve these difficulties, more petroleum-based plastics should be substituted with sustainable bio-based plastics. Renewable and natural materials that are abundant in nature are potential candidates for a wide range of polymers, which can be used to replace their synthetic counterparts. This paper focuses on some aspects of biopolymers and their classes, providing a description of starch as a main component of biopolymers, composites, and potential applications of thermoplastics starch-based in packaging application. Currently, biopolymer composites blended with other components have exhibited several enhanced qualities. The same behavior is also observed when natural fibre is incorporated with biopolymers. However, it should be noted that the degree of compatibility between starch and other biopolymers extensively varies depending on the specific biopolymer. Although their efficacy is yet to reach the level of their fossil fuel counterparts, biopolymers have made a distinguishing mark, which will continue to inspire the creation of novel substances for many years to come.

scholarly journals Formation of flavorant–propylene Glycol Adducts With Novel Toxicological Properties in Chemically Unstable E-Cigarette Liquids

2018 ◽  
Vol 21 (9) ◽  
pp. 1248-1258 ◽  
Author(s):  
Hanno C Erythropel ◽  
Sairam V Jabba ◽  
Tamara M DeWinter ◽  
Melissa Mendizabal ◽  
Paul T Anastas ◽  
...  
Keyword(s):  
Propylene Glycol ◽  
Electronic Cigarettes ◽  
Aqueous Media ◽  
Chemical Species ◽  
Resonance Spectroscopy ◽  
Reaction Products ◽  
Chemical Systems ◽  
Toxicological Effects ◽  
Wide Range ◽  
Irritant Receptors

Abstract Introduction “Vaping” electronic cigarettes (e-cigarettes) is increasingly popular with youth, driven by the wide range of available flavors, often created using flavor aldehydes. The objective of this study was to examine whether flavor aldehydes remain stable in e-cigarette liquids or whether they undergo chemical reactions, forming novel chemical species that may cause harm to the user. Methods Gas chromatography was used to determine concentrations of flavor aldehydes and reaction products in e-liquids and vapor generated from a commercial e-cigarette. Stability of the detected reaction products in aqueous media was monitored by ultraviolet spectroscopy and nuclear magnetic resonance spectroscopy, and their effects on irritant receptors determined by fluorescent calcium imaging in HEK-293T cells. Results Flavor aldehydes including benzaldehyde, cinnamaldehyde, citral, ethylvanillin, and vanillin rapidly reacted with the e-liquid solvent propylene glycol (PG) after mixing, and upward of 40% of flavor aldehyde content was converted to flavor aldehyde PG acetals, which were also detected in commercial e-liquids. Vaping experiments showed carryover rates of 50%–80% of acetals to e-cigarette vapor. Acetals remained stable in physiological aqueous solution, with half-lives above 36 hours, suggesting they persist when inhaled by the user. Acetals activated aldehyde-sensitive TRPA1 irritant receptors and aldehyde-insensitive TRPV1 irritant receptors. Conclusions E-liquids are potentially reactive chemical systems in which new compounds can form after mixing of constituents and during storage, as demonstrated here for flavor aldehyde PG acetals, with unexpected toxicological effects. For regulatory purposes, a rigorous process is advised to monitor the potentially changing composition of e-liquids and e-vapors over time, to identify possible health hazards. Implications This study demonstrates that e-cigarette liquids can be chemically unstable, with reactions occurring between flavorant and solvent components immediately after mixing at room temperature. The resulting compounds have toxicological properties that differ from either the flavorants or solvent components. These findings suggest that the reporting of manufacturing ingredients of e-liquids is insufficient for a safety assessment. The establishment of an analytical workflow to detect newly formed compounds in e-liquids and their potential toxicological effects is imperative for regulatory risk analysis.

scholarly journals Cocrystals of Ethenzamide With 2-Nitrobenzoic Acid - Conformational Analysis, MD Simulations And DFT Investigations

2021 ◽  
Author(s):  
Y. Sheena Mary ◽  
Y. Shyma Mary ◽  
Razieh Razavi
Keyword(s):  
Hydrogen Bond ◽  
Conformational Analysis ◽  
Crystal Engineering ◽  
Energy Charge ◽  
Thermodynamic Characteristics ◽  
Md Simulations ◽  
Pharmaceutical Chemistry ◽  
Nitrobenzoic Acid ◽  
Wide Range ◽  
Stability Energy

Abstract In crystal engineering and pharmaceutical chemistry, cocrystals have a wide range of applications. Ethenzamide (EA) is found to form cocrystal with 2-nitrobenzoic acid (NBA). Geometry properties like stability energy, charge distribution, bond length, electronic properties and thermodynamic characteristics have been analyzed. The C-H…O hydrogen bond involves C-H of EA and oxygen of NBA. Configuration with the angle, N3-C4-C5-C6 gives the lowest energy conformation. Partition coefficient value suggests that EA-NBA has pharmaceutics behavior. RMSD values show the simulation’s relative stability and the complexes, remained stable throughout.

scholarly journals Understanding the interaction properties of an eco-friendly corrosion inhibitor on Zn (1 1 0) surface: Comprehensive DFT-based MD simulation

2021 ◽  
Author(s):  
Atyeh Rahmanzadeh ◽  
Mahyar Rezvani ◽  
Masoud Darvish Ganji
Keyword(s):  
Interaction Energy ◽  
Active Sites ◽  
Md Simulation ◽  
Functional Materials ◽  
Metallic Surfaces ◽  
Theory Analysis ◽  
Multiple Bonds ◽  
Green Inhibitor ◽  
Wide Range ◽  
Interactive Nature

Abstract Regarding the deleterious effects of corrosion for a wide range of metals and alloys, many different techniques have been developed to protect the metals against corrosion. Utilizing organic inhibitors, especially those that contain heteroatoms and multiple bonds has been found an effective approach. In this research, the adsorption of a novel green inhibitor, Laurhydrazide N′-propan-3-one (LHP), on the Zn (110) surface was investigated using dispersion corrected DFT calculations. Interaction energy and electronic structures were calculated for different orientations of the inhibitor toward the Zn surface. The validity of calculated interaction energy has been verified by the MP2 level of theory. The AIM theory analysis revealed that LHP bound strongly to the Zn surface through its O active site and also its orientation affects greatly the interaction energy. Furthermore, diffusion of LHP through its O atoms active sites was observed with the state-of-the-art DFT-MD simulation during the simulation procedure that agrees well with the experiments for similar molecules adsorbed on the metal surfaces. The presented findings afford a vital insight into the interactive nature of adsorbed inhibitors on metallic surfaces and will help to develop advanced functional materials in coating technologies.

scholarly journals Bio-Templating: An Emerging Synthetic Technique for Catalysts. A Review

Catalysts ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1364
Author(s):  
M. Carmen Herrera-Beurnio ◽  
Jesús Hidalgo-Carrillo ◽  
Francisco J. López-Tenllado ◽  
Juan Martin-Gómez ◽  
Rafael C. Estévez ◽  
...  
Keyword(s):  
Active Sites ◽  
Experimental Studies ◽  
Functional Materials ◽  
Inorganic Materials ◽  
Hierarchical Organization ◽  
Materials Synthesis ◽  
Energy Capture ◽  
Wide Range ◽  
Mineralization Processes ◽  
And Storage

In the last few years, researchers have focused their attention on the synthesis of new catalyst structures based on or inspired by nature. Biotemplating involves the transfer of biological structures to inorganic materials through artificial mineralization processes. This approach offers the main advantage of allowing morphological control of the product, as a template with the desired morphology can be pre-determined, as long as it is found in nature. This way, natural evolution through millions of years can provide us with new synthetic pathways to develop some novel functional materials with advantageous properties, such as sophistication, miniaturization, hybridization, hierarchical organization, resistance, and adaptability to the required need. The field of application of these materials is very wide, covering nanomedicine, energy capture and storage, sensors, biocompatible materials, adsorbents, and catalysis. In the latter case, bio-inspired materials can be applied as catalysts requiring different types of active sites (i.e., redox, acidic, basic sites, or a combination of them) to a wide range of processes, including conventional thermal catalysis, photocatalysis, or electrocatalysis, among others. This review aims to cover current experimental studies in the field of biotemplating materials synthesis and their characterization, focusing on their application in heterogeneous catalysis.

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