Point interactions for 3D sub-Laplacians

In this paper we show that, for a sub-Laplacian Δ on a 3-dimensional manifold M, no point interaction centered at a point $q_0\in M$ exists. When M is complete w.r.t. the associated sub-Riemannian structure, this means that Δ acting on $C_0^{\infty }(M?\{q_0\})$ is essentially self-adjoint in $L^2(M)$. A particular example is the standard sub-Laplacian on the Heisenberg group. This is in stark contrast with what happens in a Riemannian manifold N, whose associated Laplace-Beltrami operator acting on $C_0^{\infty }(N?\{q_0\})$ is never essentially self-adjoint in $L^2(N)$, if $\dim ?N\le 3$. We then apply this result to the Schrödinger evolution of a thin molecule, i.e., with a vanishing moment of inertia, rotating around its center of mass.     

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

The topology of the molecular electron density of benzene dithiol gold cluster complex Au₄−S−C₆H₄−S′−Au′₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.     

Synthesis of Functionalized Tetrahydropyridines by SnCl4-Mediated [4+2] Cycloaddition between Donor–Acceptor Cyclobutanes and Nitriles

Cycloadditions of strained carbocycles promoted by Lewis acids are powerful methods to construct heterocyclic frameworks. In fact, the formal [3+2] cycloadditions of donor–acceptor (DA) cyclopropanes with nitriles has seen particular success in synthesis. In this work, we report on the first [4+2] cycloaddition of nitriles with DA cyclobutanes by Lewis acid activation. Tetrahydropyridine derivatives were obtained in up to 91 % yield from various aryl-activated cyclobutane diesters and aliphatic or aromatic nitriles.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.     

Recent developments of di-amide/imide-containing small molecular non-fullerene acceptors for organic solar cells

Non-fullerene organic solar cells have received increasing attentions in these years, and great progresses have been made since 2013. Among them, aromatic di-amide/imide-containing frameworks have shown promising applications. The outstanding properties of them are highly associated with their unique electronic and structural features, such as strong electron-withdrawing nature, broad absorption in UV-visible region, tunable HOMO/LUMO energy levels, easy modifications, and excellent chemical, thermal and photochemical stabilities. In this review, we give an overview of recent developments of aromatic diamide/imide-containing small molecules used as electron acceptors for organic solar cells.     

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π‐conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large‐scale synthesis of protected quarter‐, sexi‐, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single‐crystal X‐ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide‐substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

Recent Progress of Small-Molecule Ratiometric Fluorescent Probes for Peroxynitrite in Biological Systems

Peroxynitrite (ONOO⁻) as a major reactive oxygen species plays important roles in cellular signal transduction and homeostatic regulation. Precise detection of ONOO⁻ in biological systems is vital for exploring its physiological and pathological function. Among numerous detection methods, fluorescence imaging technology using fluorescent probes offers some advantages, including simple operation, high sensitivity and selectivity, as well as real-time and nondestructive detection. In particular, ratiometric fluorescent probes, in which the built-in calibration of the two emission bands prevents interference from the biological environment, have been extensively employed to monitor the fluctuation of bioactive species. In this review, we will discuss small-molecule ratiometric fluorescent probes for ONOO⁻ in live cells or in vivo, which involves chemical structures, response mechanisms, and biological applications. Moreover, the challenges and future prospects of ONOO⁻-responsive ratiometric fluorescent probe are also proposed.     

Advances towards Cell-Specific Gene Transfection: A Small-Molecule Approach Allows Order-of-Magnitude Selectivity

A transfection vector that can home in on tumors is reported. Whereas previous vectors that allow moderately cell selective gene transfection used larger systems, this small-molecule approach paved the way for precise structure-activity relationship optimization. For this, biotin, which mediates cell selectivity, was combined with the potent DNA-binding motif tetralysine-guanidinocarbonypyrrol via a hydrophilic linker, thus enabling SAR-based optimization. The new vector mediated biotin receptor (BR)-selective transfection of cell lines with different BR expression levels. Computer-based analyses of microscopy images revealed a preference of one order of magnitude for the BR-positive cell lines over the BR-negative controls.