Molecular Frameworks Research Articles

Efficient photocatalytic hydrogen evolution: Linkage units engineering in triazine-based conjugated porous polymers

Conjugated porous polymers (CPPs) have been widely reported as promising photocatalysts. However, the realization of powerful photocatalytic hydrogen production performance still benefits from the rational design of molecular frameworks and the appropriate choice of building monomers. Herein, we synthesized two novel conjugated porous polymers (CPPs) by copolymerizing pyrene and 1,3,5-triazine building blocks. It is found that minor structural changes in the peripheral groups of the triazine units can greatly affect the photocatalytic activity of the polymers. Compared with the phenyl-linkage unit, the thiophene-linkage unit can give CPP a wider absorption range of visible light, a narrower band gap, a higher transmission and separation efficiency of photo-generated carriers (electrons/holes), and a better interface contact with the photocatalytic reaction solution. The catalyst containing thiophene-triazine (ThPy-CPP) has an efficient photocatalytic hydrogen evolution rate of 21.65 and 16.69 mmol g−1h−1 under full-arc spectrum and visible light without the addition of a Pt co-catalyst, respectively, much better than the one containing phenyl-triazine (PhPy-CPP, only 5.73 and 3.48 mmol g−1h−1). This study provides a promising direction to design and construct highly efficient, cost-effective CPP-based photocatalysts, for exploring the application of noble metal-free catalysts in photocatalytic hydrogen evolution.

Reversible Metal and Ligand Redox Chemistry in Two-Dimensional Iron-Organic Framework for Sustainable Lithium-Ion Batteries.

Metal-organic frameworks (MOFs) are emerging as attractive electrode materials for lithium-ion batteries, owing to their fascinating features of sustainable resources, tunable chemical components, flexible molecular skeletons, and renewability. However, they are faced with a limited number of redox-active sites and unstable molecular frameworks during electrochemical processes. Herein, we design a novel two-dimensional (2D) iron(III)-tetraamino-benzoquinone (Fe-TABQ) with dual redox centers of Fe cations and TABQ ligands for high-capacity and stable lithium storage. It is constructed of square-planar Fe-N2O2 linkages and phenylenediamine building blocks, between which the Fe-TABQ chains are connected by multiple hydrogen bonds, and then featured as an extended π-d-conjugated 2D structure. The redox chemistry of both Fe3+ cations and TABQ anions is revealed to render its remarkable specific capacity of 251.1 mAh g-1. Benefiting from the intrinsic robust Fe-N(O) bonds and reinforced Li-N(O) bonds during cycling, Fe-TABQ delivers high capacity retentions over 95% after 200 cycles at various current densities. This work will enlighten more investigations for the molecular designs of advanced MOF-based electrode materials.

Understanding molecular and electrochemical charge transfer: theory and computations.

Electron, proton, and proton-coupled electron transfer (PCET) are crucial elementary processes in chemistry, electrochemistry, and biology. We provide here a gentle overview of retrospective and currently developing theoretical formalisms of chemical, electrochemical and biological molecular charge transfer processes, with examples of how to bridge electron, proton, and PCET theory with experimental data. We offer first a theoretical minimum of molecular electron, proton, and PCET processes in homogeneous solution and at electrochemical interfaces. We illustrate next the use of the theory both for simple electron transfer processes, and for processes that involve molecular reorganization beyond the simplest harmonic approximation, with dissociative electron transfer and inclusion of all charge transfer parameters. A core example is the electrochemical reduction of the S2O82- anion. This is followed by discussion of core elements of proton and PCET processes and the electrochemical dihydrogen evolution reaction on different metal, semiconductor, and semimetal (say graphene) electrode surfaces. Other further focus is on stochastic chemical rate theory, and how this concept can rationalize highly non-traditional behaviour of charge transfer processes in mixed solvents. As a second major area we address ("long-range") chemical and electrochemical electron transfer through molecular frameworks using notions of superexchange and hopping. Single-molecule and single-entity electrochemistry are based on electrochemical scanning probe microscopies. (In operando) scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) are particularly emphasized, with theoretical notions and new molecular electrochemical phenomena in the confined tunnelling gap. Single-molecule surface structure and electron transfer dynamics are illustrated by self-assembled thiol molecular monolayers and by more complex redox target molecules. This discussion also extends single-molecule electrochemistry to bioelectrochemistry of complex redox metalloproteins and metalloenzymes. Our third major area involves computational overviews of molecular and electronic structure of the electrochemical interface, with new computational challenges. These relate to solvent dynamics in bulk and confined space (say carbon nanostructures), electrocatalysis, metallic and semiconductor nanoparticles, d-band metals, carbon nanostructures, spin catalysis and "spintronics", and "hot" electrons. Further perspectives relate to metal-organic frameworks, chiral surfaces, and spintronics.

J-Aggregation induced NIR-II fluorescence: an aza-BODIPY luminogen for efficient phototheranostics.

The development of organic dyes with emission peaks in the second near-infrared window (NIR-II 1000-1700 nm) is highly desirable for in vivo imaging and imaging-guided phototheranostics. However, the lack of appropriate molecular frameworks and the challenges associated with complex synthesis critically hinder the development of new candidate fluorophores. J-Aggregation is considered as a smart and straightforward way to construct such a therapeutic agent with NIR-II fluorescence imaging properties. Here, we present the design and synthesis of an aza-BODIPY probe (TA). Upon encapsulation within the amphiphilic polymer DSPEG-PEG2000-NH2, TA underwent self-assembly and formed J-aggregates (TAJ NPs), which showed emission at 1020 nm. High spatial resolution and adequate signal-to-noise ratio of the TAJ NPs are demonstrated for noninvasive bioimaging of the vasculature, lymph nodes and bones of mice in the NIR-II region. Moreover, the TAJ NPs exhibited good tumor enrichment efficiency with reduced liver accumulation and significant imaging-guided phototherapy performance against lung cancer cells. Taken together, this work not only introduces a new NIR-II imaging and phototheranostic agent based on J-aggregates, but also provides insight into the development of versatile organic dyes for future clinical implementation.

Machine learning of isomerization in porous molecular frameworks: exploring functional group pair distance distributions

All possible isomers of a pore in a functionalized molecular framework material may be represented as a single histogram, showing the distances between functional groups.

SYNTHESIS AND CHARATERIZATIONS OF THE SCHIFF BASE DERIVED FROM 2-HYDROXY-5-NITROBENZALDEHYDE ALONGWITH HIRSHFELD SURFACE ANALYSIS AND COMPUTATIONAL STUDY

The current research work is about the synthesis of the novel Schiff base obtained by the condensation reaction of 2-hydroxy-5-nıtrobenzaldehyde with 3-fluoroaniline. The synthesized compound is characterized by IR spectroscopy and single crystal X-rays diffraction (SC-XRD) technique. SC-XRD inferred that CHO and off-set π π stacking interactions are the main features of the supramolecular assembly. Hirshfeld surface analysis is performed to shield more light on the intermolecular interactions. Mechanical strength of the crystal is predicted by the void analysis. Moreover, the interaction energy between molecular pairs and energy frameworks are computed by using B3LYP/6-31G(d,p) electron density model in order to understand the topology of the crystal.

Fluctuations of conserved charges in hydrodynamics and molecular dynamics

We present an overview of recent theoretical results on fluctuations of conserved charges in heavy-ion collisions obtained in relativistic hydrodynamics and molecular dynamics frameworks. In particular, we discuss the constraints on the location of the QCD critical point based on comparisons of experimental data on proton number cumulants with precision calculations of noncritical contributions. We also cover recent developments on critical fluctuations in molecular dynamics simulations.

Naphthyl bearing 1,3,4-thiadiazoleacetamides targeting the parasitic folate pathway as anti-infectious agents: in silico, synthesis, and biological approach.

Malaria is still a complex and lethal parasitic infectious disease, despite the availability of effective antimalarial drugs. Resistance of malaria parasites to current treatments necessitates new antimalarials targeting P. falciparum proteins. The present study reported the design and synthesis of a series of a 2-(4-substituted piperazin-1-yl)-N-(5-((naphthalen-2-yloxy)methyl)-1,3,4-thiadiazol-2-yl)acetamide hybrids for the inhibition of Plasmodium falciparum dihydrofolate reductase (PfDHFR) using computational biology tools followed by chemical synthesis, structural characterization, and functional analysis. The synthesized compounds were evaluated for their in vitro antimalarial activity against CQ-sensitive PfNF54 and CQ-resistant PfW2 strain. Compounds T5 and T6 are the most active compounds having anti-plasmodial activity against PfNF54 with IC50 values of 0.94 and 3.46 μM respectively. Compound T8 is the most active against the PfW2 strain having an IC50 of 3.91 μM. Further, these active hybrids (T5, T6, and T8) were also evaluated for enzyme inhibition assay against PfDHFR. All the tested compounds were non-toxic against the Hek293 cell line with good selectivity indices. Hemolysis assay also showed non-toxicity of these compounds on normal uninfected human RBCs. In silico molecular docking studies were carried out in the binding pocket of both the wild-type and quadruple mutant Pf-DHFR-TS to gain further insights into probable modes of action of active compounds. ADME prediction and physiochemical properties support their drug-likeness. Additionally, they were screened for antileishmanial activity against L. donovani promastigotes to explore broader applications. Thus, this study provides molecular frameworks for developing potent antimalarials and antileishmanial agents.

Harnessing ion–dipole interactions: a simple and effective approach to high-performance lithium receptors

Incorporating strong ion–dipole interactions within acyclic molecular frameworks can remarkably enhance both binding affinity and selectivity for lithium ion, offering a simple and effective strategy for developing high-performance lithium receptors.

Resistance is futile: targeting multidrug-resistant bacteria with de novo Cys-rich cyclic polypeptides.

The search for novel antimicrobial agents to combat microbial pathogens is intensifying in response to rapid drug resistance development to current antibiotic therapeutics. The use of disulfide-rich head-to-tail cyclized polypeptides as molecular frameworks for designing a new type of peptide antibiotics is gaining increasing attention among the scientific community and the pharmaceutical industry. The use of macrocyclic peptides, further constrained by the presence of several disulfide bonds, makes these peptide frameworks remarkably more stable to thermal, biological, and chemical degradation showing better activities when compared to their linear analogs. Many of these novel peptide scaffolds have been shown to have a high tolerance to sequence variability in those residues not involved in disulfide bonds, able to cross biological membranes, and efficiently target complex biomolecular interactions. Hence, these unique properties make the use of these scaffolds ideal for many biotechnological applications, including the design of novel peptide antibiotics. This article provides an overview of the new developments in the use of several disulfide-rich cyclic polypeptides, including cyclotides, θ-defensins, and sunflower trypsin inhibitor peptides, among others, in the development of novel antimicrobial peptides against multidrug-resistant bacteria.

Luminescent organic molecular frameworks from tetraphenylethylene-based building blocks

In this review, we mainly summarize the emerging luminescent organic molecular frameworks consisting of hydrogen bonded frameworks and supramolecular organic frameworks based on tetraphenylethylene building blocks.

A TADF Emitter with Dual Para-Positioned Donors Enables OLEDs with Improved Efficiency and CIE Coordinates Close to the Rec. 2020 Red Standard

Developing red thermally activated delayed fluorescence (TADF) emitters concurrently with high efficiency and emission color close to the BT.2020 red standard is an ongoing challenge. Herein, we developed a new red TADF emitter BCN-TPA, in which two identical donors are attached at the para-positions of one fused phenyl ring in the acceptor framework. Such an arrangement mode can lead the donors with an obvious superimposed effect comparing the conventional arrangement with edge-capped donors on the acceptor. Thus, BCN-TPA yields enhanced overall donor strength with numerous superiorities, such as high oscillator strength and narrow singlet-triplet energy difference, thus giving rise to red-shifted emission with improved overall exciton utilization. In an organic light-emitting diode, BCN-TPA presents efficient deep-red electroluminescence with a maximum external quantum efficiency of 27.6% and a peak at 656 nm, corresponding to CIE coordinates of (0.686, 0.304), which are very close to the red primary in the BT.2020 standard. To the best of our knowledge, this is one of the topmost efficiencies in the field of deep-red TADF OLEDs. This work exemplifies an easy design principle for constructing high-performance deep-red TADF emitters, providing unique molecular-level insights toward improving color quality and elevating efficiency based on conventional D-A type molecular frameworks.

Molecular Framework Analysis of the Generated Database GDB-13s.

The generated databases (GDBs) list billions of possible molecules from systematic enumeration following simple rules of chemical stability and synthetic feasibility. To assess the originality of GDB molecules, we compared their Bemis and Murcko molecular frameworks (MFs) with those in public databases. MFs result from molecules by converting all atoms to carbons, all bonds to single bonds, and removing terminal atoms iteratively until none remain. We compared GDB-13s (99,394,177 molecules up to 13 atoms containing simplified functional groups, 22,130 MFs) with ZINC (885,905,524 screening compounds, 1,016,597 MFs), PubChem50 (100,852,694 molecules up to 50 atoms, 1,530,189 MFs), and COCONUT (401,624 natural products, 42,734 MFs). While MFs in public databases mostly contained linker bonds and six-membered rings, GDB-13s MFs had diverse ring sizes and ring systems without linker bonds. Most GDB-13s MFs were exclusive to this database, and many were relatively simple, representing attractive targets for synthetic chemistry aiming at innovative molecules.

Photostable Small-Molecule NIR-II Fluorescent Scaffolds that Cross the Blood-Brain Barrier for Noninvasive Brain Imaging.

The second near-infrared (NIR-II, 1000-1700 nm) fluorescent probes have significant advantages over visible or NIR-I (600-900 nm) imaging for both depth of penetration and level of resolution. Since the blood-brain barrier (BBB) prevents most molecules from entering the central nervous system, NIR-II dyes with large molecular frameworks have limited applications for brain imaging. In this work, we developed a series of boron difluoride (BF2) formazanate NIR-II dyes, which had tunable photophysical properties, ultrahigh photostability, excellent biological stability, and strong brightness. Modulation of the aniline moiety of BF2 formazanate dyes significantly enhances their abilities to cross the BBB for noninvasive brain imaging. Furthermore, the intact mouse brain imaging and dynamic dye diffusion across the BBB were monitored using these BF2 formazanate dyes in the NIR-II region. In murine glioblastoma models, these dyes can differentiate tumors from normal brain tissues. We anticipate that this new type of small molecule will find potential applications in creating probes and drugs relevant to theranostic for brain pathologies.

Biological aspects of nitrogen heterocycles for amyotrophic lateral sclerosis.

Amyotrophic lateral sclerosis (ALS) is a rare, cumulative neurological deteriorating disease that disturbs the neurons (nerve cells) that control voluntary muscle movement (those muscles we choose to move). Currently, the Food and Drug Administration (FDA) approved drugs such as Radicava, Rilutek, Tiglutik, Exservan, and Nuedexta to treat ALS. Given the wide range of pharmaceutical applications of heterocyclic compounds, especially those containing the nitrogen ring systems such as pyridine, pyrimidine, and indole. These molecular frameworks have piqued the interest of medicinal chemists for further investigation in a variety of diseases. We have found several review works done on this research topic. Until now, no reviews published on the nitrogen heterocycles for treating ALS. This review examines the major causes of ALS, a brief history of medications that have been used to treat it so far, and the most recent breakthroughs in nitrogen ring systems for treating ALS. The novelty of this study provides insights on several effective synthetic techniques for nitrogen-based heterocyclic medications that operate as potent anti-inflammatory treatments and guard against ALS. KEY POINTS: • Pharmacological activity of heterocyclic compounds. • Neurodegenerative diseases and their drawbacks are discussed in detail. • Recent survey of nitrogen heterocycles in treating ALS disease are highlighted.

Cobalt-Catalyzed Nitrogen Atom Insertion in Arylcycloalkenes.

Developing strategies enabling the modification of underlying molecular frameworks facilitates access to underexplored chemical spaces. Skeletal editing is an emerging technology for late-stage diversification of bioactive molecules. However, the current state of this knowledge remains undeveloped. This work describes a simple protocol that "inserts" a nitrogen atom into arylcycloalkenes to form the corresponding N-heterocycles. The use of an inexpensive cobalt catalyst under aqueous and open-air conditions makes this protocol very practical. Examples of late-stage modification of compounds of pharmaceutical interest and complex fused ring compounds further demonstrated the potentially broad applicability of this methodology.

Atroposelective Synthesis of Tetrahydropyrrolo[3,2‐c]azepine Derivatives Through Gold(I)‐Catalyzed Hydroarylation

AbstractA series of enantioenriched substituted tetrahydropyrrolo[3,2‐c]azepine products possessing an axial chirality were synthesized in 63–99% yield through a gold(I)‐catalyzed hydroarylation. DFT calculations rationalized the reactivity observed for the formation of such complex molecular frameworks and guided our choice in the pyrrole N‐substituent to isolate configurationally stable compounds.magnified image

Merging Rh-Catalyzed C-H Functionalization and Cascade Cyclization to Enable Propargylic Alcohols as Three-Carbon Synthons.

Reported herein is a reactivity of propargyl alcohols as "Three-Carbon Synthons" in a Rh(III)-catalyzed C-H functionalization of acetanilides, leading to the synthesis of core structures of isocryptolepine, γ-carbolines, dihydrochromeno[2,3-b]indoles, and diindolylmethanes (DIM) derivatives. The transformation involves a rhodium(III)-catalyzed C-H functionalization and heteroannulation to yield indoles followed by a cascade cyclization with both external and internal nucleophiles to afford diverse products. The role of the hydroxy group, the key function of the silver additive, the origin of the reverse regioselectivity and the rate-determining step, are rationalized in conformity with the combination of experimental, noncovalent interaction analysis and DFT studies. This protocol is endowed with several salient features, including one-pot multistep cascade approach, exclusive regioselectivity, good functional group tolerance and synthesis of variety of molecular frameworks.

Quest of new molecular frameworks for photoinduced carbon monoxide-releasing molecules: a computational prospective

Quest of new molecular frameworks for photoinduced carbon monoxide-releasing molecules: a computational prospective

Maneuvering Applications of Covalent Organic Frameworks via Framework-Morphology Modulation.

Translating the performance of covalent organic frameworks (COFs) from laboratory to macroscopic reality demands specific morphologies. Thus, the advancement in morphological modulation has recently gained some momentum. A clear understanding of nano- to macroscopic architecture is critical to determine, optimize, and improve performances of this atomically precise porous material. Along with their chemical compositions and molecular frameworks, the prospect of morphology in various applications should be discussed and highlighted. A thorough insight into morphology versus application will help produce better-engineered COFs for practical implications. 2D and 3D frameworks can be transformed into various solids such as nanospheres, thin films, membranes, monoliths, foams, etc., for numerous applications in adsorption, separation photocatalysis, the carbon dioxide reduction, supercapacitors, and fuel cells. However, the research on COF chemistry mainly focuses on correlating structure to property, structure to morphology, and structure to applications. Here, critical insights on various morphological evolution and associated applications are provided. In each case, the underlying role of morphology is unveiled. Toward the end, a correlation between morphology and application is provided for the future development of COFs.