Ligand Design to Acquire Specificity to Intended G-Quadruplex Structures

A G-quadruplex is a nucleic acid secondary structure that is adopted by guanine-rich sequences, and is considered to be relevant in various pharmacological and biological contexts. G-Quadruplexes have also attracted great attention in the field of DNA nanotechnology because of their extremely high thermal stability and the availability of many defined structures. To date, a large repertory of DNA/RNA G-quadruplex-interactive ligands has been developed by numerous laboratories. Several relevant reviews have also been published that have helped researchers to grasp the full scope of G-quadruplex research from its outset to the present. This review focuses on the G-quadruplex ligands that allow targeting of specific G-quadruplexes. Moreover, unique ligands, successful methodologies, and future perspectives in relation to specific G-quadruplex recognition are also addressed.     

Molecular Acceptors Based on a Triarylborane Core Unit for Organic Solar Cells

Triarylboranes that exhibit p–π* conjugation serve as versatile building blocks to design n-type organic/polymer semiconductors. A series of new molecular acceptors based on triarylborane is reported here. These molecules are designed with a boron atom that bears a bulky 2,4,6-tri-tert-butylphenyl (Mes*) substituent at the core and strong electron-withdrawing 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) units as the end-capping groups that are linked to the core by bithiophene bridges. Butyl or butoxy groups are introduced to the bithiophene units to tune the optoelectronic properties. These molecules show nearly planar backbones with highly localized steric hindrance at the core, low LUMO/HOMO energy levels, and broad absorption bands spanning the visible region, which are all very desirable characteristics for use as electron acceptors in organic solar cell (OSC) applications. The attachment of butyl groups to the bithiophene bridges brings about a slightly twisted backbone, which in turn promotes good solubility and homogeneous donor/acceptor blend morphology, whereas the introduction of butoxy groups leads to improved planarity, favorable stacking in the film state, and a greatly reduced band gap. OSC devices based on these molecules exhibit encouraging photovoltaic performances with power conversion efficiencies reaching up to 4.07 %. These results further substantiate the strong potential of triarylboranes as the core unit of small molecule acceptors for OSC applications.     

Probing molecular environments with a fictitious isotopic dipole

A HD-like (HD: mono-deuterated hydrogen molecule) isotopic dipole moment is proposed as a sensible probe for molecular environments, in particular for electrostatic fields and polarizable (reactive) sites of molecules. Fictitious nuclear masses are chosen in order to yield a rigid dipole with a small appropriate magnitude. Upon subtracting the Born-Oppenheimer energy, the interaction is reduced to field-dipole-like and dipole-polarizability-like terms, the last one being particularly informative since connected to potentially reactive sites. Possible asymmetries of this term appear as signatures of charged sites in the molecule. The field strength and orientation are easily obtained by identifying the minimum field-dipole energy configuration and flipping the dipole from it. Tests with hydrogen, water, benzene, and chlorobenzene molecules confirm the good performance of the method. In an application to test the present models for hydrogen activation by a frustrated Lewis pair, the full potential of the method is assessed.     

Targeted Construction of Amorphous MoSx with an Inherent Chain Molecular Structure for Improved Pseudocapacitive Lithium-Ion Response

Owing to low ion/electron conductivity and large volume change, transitional metal dichalcogenides (TMDs) suffer from inferior cycle stability and rate capability when used as the anode of lithium-ion batteries (LIBs). To overcome these disadvantages, amorphous molybdenum sulfide (MoS_x) nanospheres were prepared and coated with an ultrathin carbon layer through a simple one-pot reaction. Combining X-ray photoelectron spectroscopy (XPS) with theoretical calculations, MoS_x was confirmed as having a special chain molecular structure with two forms of S bonding (S²⁻ and S₂²⁻), the optimal adsorption sites of Li⁺ were located at S₂²⁻. As a result, the MoS_x electrode exhibits superior cycle and rate capacities compared with crystalline 2H-MoS₂ (e.g., delivering a high capacity of 612.4 mAh g⁻¹ after 500 cycles at 1 A g⁻¹). This is mainly attributed to more exposed active S₂²⁻ sites for Li storage, more Li⁺ transfer pathways for improved ion conductivity, and suppressed electrode structure pulverization of MoS_x derived from the inherent chain-like molecular structure. Quantitative charge storage analysis further demonstrates the improved pseudocapacitive contribution of amorphous MoS_x induced by fast reaction kinetics. Moreover, the morphology contrast after cycling demonstrates the dispersion of active materials is more uniform for MoS_x than 2H-MoS₂, suggesting the MoS_x can well accommodate the volume stress of the electrode during discharging. Through regulating the molecular structure, this work provides an effective targeted strategy to overcome the intrinsic issues of TMDs for high-performance LIBs.     

Two weight commutators in the Dirichlet and Neumann Laplacian settings

In this paper we establish the characterization of the weighted BMO via two weight commutators in the settings of the Neumann Laplacian ${\mathrm{\Delta }}_{N_{+}}$ on the upper half space ${\mathbb{R}}_{+}^n$ and the reflection Neumann Laplacian ${\mathrm{\Delta }}_N$ on ${\mathbb{R}}^n$ with respect to the weights associated to ${\mathrm{\Delta }}_{N_{+}}$ and ${\mathrm{\Delta }}_N$ respectively. This in turn yields a weak factorization for the corresponding weighted Hardy spaces, where in particular, the weighted class associated to ${\mathrm{\Delta }}_N$ is strictly larger than the Muckenhoupt weighted class and contains non-doubling weights. In our study, we also make contributions to the classical Muckenhoupt–Wheeden weighted Hardy space (BMO space respectively) by showing that it can be characterized via the area function (Carleson measure respectively) involving the semigroup generated by the Laplacian on ${\mathbb{R}}^n$ and that the duality of these weighted Hardy and BMO spaces holds for Muckenhoupt $A^p$ weights with $p\in (1,2]$ while the previously known related results cover only $p\in (1,\frac{n+1}{n}]$. We also point out that this two weight commutator theorem might not be true in the setting of general operators L, and in particular we show that it is not true when L is the Dirichlet Laplacian ${\mathrm{\Delta }}_{D_{+}}$ on ${\mathbb{R}}_{+}^n$.     

Synthesis of Pure Silica MWW Zeolite in Fluoride Medium by Using an Imidazolium-Based Long Dication

As the spacer length in 1,2-dimethylimidazolium-based dications increases beyond a specific point (six methylene units), they fail in structure-directing towards STW zeolites in any synthetic conditions. These dications can instead produce, under fluoride concentrated conditions, either *BEA [in the case of the eight-methylene-unit structure-directing agent (SDA)] or MWW (ten methylene units) zeolites. For any length of the dication, the default zeolite (MTW) is a relatively dense zeolite containing a unidimensional channel, whereas the zeolite demanding most specificity (STW, *BEA or MWW) is more porous, affording a larger concentration of the dication to be occluded. This work provides the first reported fluoride synthesis of pure silica MWW zeolites. Charge balance of the organic dications in this zeolite was achieved by combining “structural” silanolates, regular “connectivity defects” and occluded fluoride. Molecular mechanics calculations showed a perfect fit of the decamethylenebis(dimethylimidazolium) dication in the sinusoidal intralayer pore system of MWW. The calculations showed also that the dication is able to stabilize the interlayer space without disturbing the hydrogen-bonding system that holds the layers together in the as-made material. The ¹⁹F magic-angle spinning (MAS) NMR presented two distinct resonances at −71 and −83 ppm, which, on the basis of DFT calculations, we tentatively assigned to fluoride occluded in [4⁶6²] and [4¹5²6²] cages of the MWW structure, respectively. The same DFT study determines a different chemical shift of one methyl ¹³C nuclear magnetic resonance according to the imidazolium ring residing in the sinusoidal channels or in the large cup cavities, thus explaining an experimentally observed splitting of that resonance.     

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.     

Lipid Switches: Stimuli-Responsive Liposomes through Conformational Isomerism Driven by Molecular Recognition

Advancements in the field of liposomal drug carriers have culminated in greatly improved delivery properties. An important aspect of this work entails development of designer liposomes for release of contents triggered by environmental changes. The majority of these systems are driven by chemical reactions in the presence of different stimuli. However, a promising new paradigm instead focuses on molecular recognition events as the impetus for content release. In certain cases, these platforms exploit synthetic lipid switches designed to undergo conformational changes upon binding to target ions or molecules that perturb membrane assembly, thereby triggering cargo release. Examples of this approach reported thus far showcase how rational design of lipid switches can result in dramatic changes in lipid assembly properties. These strategies show great promise for opening up new pathophysiological stimuli that can be harnessed for programmed content release in drug delivery applications.     

Size‐Dependence of the Melting Temperature of Individual Au Nanoparticles

Nanoparticles have an immense importance in various fields, such as medicine, catalysis, and various technological applications. Nanoparticles exhibit a significant depression in melting point as their size goes below ≈10 nm. However, nanoparticles are frequently used in high temperature applications such as catalysis where temperatures often exceed several 100 degrees which makes it interesting to study not only the melting temperature depression, but also how the melting progresses through the particle. Using high‐resolution transmission electron microscopy, the melting process of gold nanoparticles in the size range of 2–20 nm Au nanoparticles combined with molecular dynamics studies is investigated. A linear dependence of the melting temperature on the inverse particle size is confirmed; electron microscopy imaging reveals that the particles start melting at the surface and the liquid shell formed then rapidly expands to the particle core.