: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Covalent organic frameworks (COFs) as an emerging class of crystalline porous materials have received much attention due to their tunable porosity, modifiable skeletons, and atomically precise structures. Besides, COFs can provide multiple high-rate charge carrier transport (electron, hole, and ion) pathways, including conjugated skeletons, overlapped π electron clouds among the stacked layers, and open channels with a variable chemical environment. Therefore, they have shown great potential in electrochemical energy storage (EES) and conversion (EEC). However, in bulk COFs, the defects always impede charge carrier conduction, and the difficulties in reaching deep-buried active sites by either electrons or ions lead to limited performance. To overcome these obstacles, numerous research studies have been carried out to obtain COF nanosheets (NSs). This review first describes the preparation strategies of COF NSs via bottom-up and top-down approaches. Then, the applications of bulk COFs and COF NSs in EES and EEC are summarized, such as in batteries, supercapacitors, and fuel cells. Finally, key challenges and future directions in these areas are discussed.

Bulk COFs and COF nanosheets for electrochemical energy storage and conversion

Covalent organic frameworks offer a molecular platform for integrating organic units into periodically ordered yet extended two- and three-dimensional polymers to create topologically well-defined polygonal lattices and built-in discrete micropores and/or mesopores. This polymer architecture is unique as it enables predesigning both primary- and high-order structures, greatly enhancing our capabilities of designing organic materials to produce predictable structures and to achieve unique properties and functions. Progress over the past 15 years in the design, synthesis and functional exploration of COFs has successively established the basis of the COF field and COFs have shown the great potential of chemistry in developing a class of amazing organic materials. In this review, we focus on analysing the historic developments of COFs to uncover a full materials and application picture by providing comprehensive yet clear guidance for molecular design, synthetic control and functional exploration. We scrutinise the structural components of COFs including building blocks, reactive sites and functional groups with the aim of finding the origins of structural designability and diversity, as well as multiple functionalities. We disclose strategies for designing and synthesising frameworks to construct various tailor-made interfaces, and for exploring skeletons and pores to design properties and functions. With well-defined skeletons, pores and interfaces that offer a chemical basis to trigger and control interactions with photons, excitons, phonons, polarons, electrons, holes, spins, ions and molecules, we illustrate the current status of our understandings of structure-property correlations, and unveil the principles for establishing a regime to design unique functions that originate from and are inherent to structures. We predict the key central issues in design and synthesis, the challenges in functional design and the future directions from the perspectives of chemistry, physics and materials science.

Covalent organic frameworks: an ideal platform for designing ordered materials and advanced applications

Remarkable advances have been achieved in modern material technology, especially in device fabrication, and these have facilitated the use of diverse materials in various applications. Carbon nanotubes (CNTs) are being successfully implemented in drug delivery, sensing, water purification, composite materials, and bone scaffolds. Thus, CNTs must meet a wide range of criteria such as surface modification, high aspect ratio, desired conductivity, high porosity and loading, non-toxicity, specificity, and selectivity, and compatibility for device fabrication. The main focus of this review is to explore the maximum applications of CNTs for human health, and we particularly focus on nanocarrier and biomedical applications. The scope of this review initially covers the basic aspects of CNTs and is also extended further to describe their synthesis strategies as well as various challenges encountered in their functionalization, dispersion, and toxicity. Our discussion also emphasizes future directions for these emerging fields of research.

Carbon nanotubes: a novel material for multifaceted applications in human healthcare

Non-traditional intrinsic luminescence: inexplicable blue fluorescence observed for dendrimers, macromolecules and small molecular structures lacking traditional/conventional luminophores

Functional Silica and Carbon Nanocomposites Based on Polybenzoxazines

Hierarchically ordered mesoporous materials have gained significant scientific attention due to their high surface areas, uniform porosity over various lengths scales, high-volume storage capability, shape selectivity, enhanced mass transport and diffusion. These materials have been widely applied in the fields of photocatalysis, separation, adsorption, photovoltaic solar cells, energy storage and conversion, chemical sensing, and drug delivery. In general, hierarchically porous materials can be generated in two ways: through sol-gel template approaches and a combination of surfactant-assisted procedures. In this review, we discuss recent progress in the preparation, properties, and potential applications of four hierarchically ordered porous materials: hierarchical mesoporous silica, mesoporous phenolic/carbon, nitrogen-doped mesoporous carbon, and mesoporous/microporous covalent organic frameworks.

Construction hierarchically mesoporous/microporous materials based on block copolymer and covalent organic framework

The preparation of hybrid nanocomposite materials derived from polyhedral oligomeric silsesquioxane (POSS) nanoparticles and polyimide (PI) has recently attracted much attention from both academia and industry, because such materials can display low water absorption, high thermal stability, good mechanical characteristics, low dielectric constant, flame retardance, chemical resistance, thermo-redox stability, surface hydrophobicity, and excellent electrical properties. Herein, we discussed the various methods that have been used to insert POSS nanoparticles into PI matrices, through covalent chemical bonding and physical blending, as well as the influence of the POSS units on the physical properties of the PIs.

Mohamed Gamal Mohamed

Papers

Functional Silica and Carbon Nanocomposites Based on Polybenzoxazines

Construction hierarchically mesoporous/microporous materials based on block copolymer and covalent organic framework

Functional Polyimide/Polyhedral Oligomeric Silsesquioxane Nanocomposites

Pyrene-functionalized tetraphenylethylene polybenzoxazine for dispersing single-walled carbon nanotubes and energy storage

Solid-State Chemical Transformations to Enhance Gas Capture in Benzoxazine-Linked Conjugated Microporous Polymers