Electronic structure of strongly correlated systems: recent developments in multiconfiguration pair-density functional theory and multiconfiguration nonclassical-energy functional theory

Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn–Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin–orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals.

This feature article overviews recent work on active spaces, matrix product reference states, treatment of quasidegeneracy, hybrid theory, density-coherence functionals, machine-learned functionals, spin–orbit coupling, gradients, and dipole moments.     

Efficacious and sustained release of an anticancer drug mitoxantrone from new covalent organic frameworks using protein corona

Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices. We have introduced a perylene-based COF, PER@PDA-COF-1, which acts as an effective porous volumetric reservoir for an anticancer drug, mitoxantrone (MXT). The drug-loaded COF (MXT–PER@PDA-COF-1) exhibited zero cellular release of MXT towards cancer cells, which can be attributed to the strong intercalation between the anthracene-dione motif of the drug and the perylene-based COF backbone. Here, we have introduced a strategy involving the serum-albumin-triggered intracellular release of mitoxantrone from MXT–PER@PDA-COF-1. The serum albumin acts as an exfoliating agent and as a colloidal stabilizer in PBS medium (pH = 7.4), rapidly forming a protein corona around the exfoliated COF crystallites and inducing the sustained release of MXT from the COF into tumorigenic cells.

Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices.     

Evaluation of Electrospun PCL-PLGA for Sustained Delivery of Kartogenin

In this study, kartogenin was incorporated into an electrospun blend of polycaprolactone and poly(lactic-co-glycolic acid) (1:1) to determine the feasibility of this system for sustained drug delivery. Kartogenin is a small-molecule drug that could enhance the outcome of microfracture, a cartilage restoration procedure, by selectively stimulating chondrogenic differentiation of endogenous bone marrow mesenchymal stem cells. Experimental results showed that kartogenin did not affect the electrospinnability of the polymer blend, and it had negligible effects on fiber morphology and scaffold mechanical properties. The loading efficiency of kartogenin into electrospun membranes was nearly 100%, and no evidence of chemical reaction between kartogenin and the polymers was detected by Fourier transform infrared spectroscopy. Analysis of the released drug using high-performance liquid chromatography–photodiode array detection indicated an abundance of kartogenin and only a small amount of its major hydrolysis product. Kartogenin displayed a typical biphasic release profile, with approximately 30% being released within 24 h followed by a much slower, constant rate of release up to 28 days. Although additional development is needed to tune the release kinetics and address issues common to electrospun scaffolds (e.g., high fiber density), the results of this study demonstrated that a scaffold electrospun from biodegradable synthetic polymers is a suitable kartogenin delivery vehicle.     

Preparation of nano-hydroxyapatite/poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) biocomposite microspheres

Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).     

Fibrous twists and turns: early ceramic technology revealed through computed tomography

While the emergence of pottery manufacturing is a wide-spread historical occurrence, and one that has garnered the attention of archaeologists for decades, we know very little about how these ancient vessels were created. Through the application of radiographic scanning and computed tomography this paper provides insights into the manufacturing techniques used by the earliest potters in North America. While x-rays have been used to investigate ceramic manufacturing techniques for decades, this paper provides a reassessment of radiography in light of advances in both computed tomography and reconstructive software.     

Comparison of the growth and degradation of poly(glycolic acid) and poly(ε‐caprolactone) brushes

The growth and degradation of poly(glycolic acid) (PGA) and poly(ε‐caprolactone) (PCL) brushes were compared. Using tin (octanoate) as the catalyst, optimal conditions were found for growth of each polyester brush from the hydroxy‐terminated silicon surface via ring‐opening polymerization. PCL brushes grew thicker at elevated temperatures but the thickest PGA brushes grew at room temperature. Unlike bulk polyesters that can degrade under both acidic and basic conditions, the confined surface polyester brushes only degraded under neutral or basic conditions. The degradation mechanism of grafted polyester brushes was probed through a blocking test. It was shown that the terminal hydroxy groups of these polyester brushes were essential to the degradation process indicating a preferential backbiting mechanism. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4643–4649     

Synthesis of two dihydropyrroloindoledione‐based copolymers for organic electronics

Two novel dihydropyrroloindoledione (DPID)‐based copolymers have been synthesized in a two directional approach and characterized (gel permeation chromatography (GPC), ultraviolet‐visible (UV–vis), cyclic voltammetry, and computational models). These planar, broad absorption copolymers show promise for use in organic electronics, with deep energy levels and low bandgaps. The two‐directional Knoevenagel condensation used demonstrates the versatility of DPID as a useful yet underexploited conjugated unit. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of a (thienylethenyl)benzimidazole platinum acetylide complex

A new platinum acetylide complex based on 6-dialkylaminobenzimidazol-2-yl-vinyl-2-thiophene-5-ylethyne was synthesized in seven steps and 2% overall yield.     

Utilization of the hydroxyalkylation reaction to prepare bis(benzocrown ethers)

The hydroxyalkylation reaction has been used to condense benzocrown ethers with various aldehydes and ketones. The condensation reactions are catalyzed by triflic or sulfuric acid. The products from the reactions are bis(benzocrown ethers) and they are formed in good yields (42-98%, 13 examples).