Understanding metallophilic interactions

Metallophilic (metal–metal) interactions are weak interactions between closed-shell (d10, s2) or pseudo-closed-shell (d8) metal cations. This type of interaction is generally believed to be responsible for various intriguing structures, luminescence, catalysis and magnetism. To gain a better understanding of metallophilic interactions, both experimental and computational investigations have been carried out in this thesis. Chapter 1 gave an up-to-date literature review on the definition, significance, and methods of estimating metallophilic interactions. The disputed nature and strength of metallophilic interactions encouraged us to further understand them. Chapter 2 focused on aurophilic interactions between AuI cations. Aurophilic interactions were observed in the solid state, but not well expressed in solution. Further experimental and computational results suggested that the strength of aurophilic interactions were weaker than electrostatic interactions. The nature of aurophilic interactions arose from orbital interactions rather than dispersion. Chapter 3 presented the study of metallophilic interactions between group 10 metal centres, including PtII–PtII, PdII–PdII and NiII–NiII. A series of cyclometalated square-planar metal complexes with different metals or substituents were prepared. PtII–PtII interactions were found to be stronger than PdII–PdII and NiII–NiII interactions. The dimerization constants of the Pt-containing complexes increased in line with increasing electron-withdrawing ability. Chapter 4 investigated the solvent-induced and thermally dependent colour changes of the Pt-containing complexes synthesised in chapter 3. Metallophilic interactions were proposed to be important in influencing the luminescence properties

The Energetic Significance of Metallophilic Interactions

Metallophilic interactions are increasingly recognized as playing an important role in molecular assembly, catalysis, and bio‐imaging. However, present knowledge of these interactions is largely derived from solid‐state structures and gas‐phase computational studies rather than quantitative experimental measurements. Here, we have experimentally quantified the role of aurophilic (AuI⋅⋅⋅AuI), platinophilic (PtII⋅⋅⋅PtII), palladophilic (PdII⋅⋅⋅PdII), and nickelophilic (NiII⋅⋅⋅NiII) interactions in self‐association and ligand‐exchange processes. All of these metallophilic interactions were found to be too weak to be well‐expressed in several solvents. Computational energy decomposition analyses supported the experimental finding that metallophilic interactions are overall weak, meaning that favorable dispersion and orbital hybridization contributions from M⋅⋅⋅M binding are largely outcompeted by electrostatic or dispersion interactions involving ligand or solvent molecules. This combined experimental and computational study provides a general understanding of metallophilic interactions and indicates that great care must be taken to avoid over‐attributing the energetic significance of metallophilic interactions

Preparation and Membrane Permeability of Curcumin Nanoparticles by Subcritical Water Technology

Curcumin (Cur) nanoparticles were prepared by subcritical water (SBCW) method and its membrane permeability was evaluated. The processing conditions for the preparation of curcumin nanoparticles were investigated in terms of its particle size distribution, polydispersity index (PDI) and zeta potential, and the prepared nanoparticles were characterized and evaluated for in vitro membrane permeability. The results showed that nanoparticles with a diameter of 166 nm and a drug loading of 70.2% were obtained under the conditions: SBCW temperature 120 ℃, receiving solvent temperature 0 ℃, subcritical water/receiving solution ratio 1:3 (V/V), 0.04 g/100 mL lactose as stabilizing agent, and 30% (V/V) ethanol as entrainer. Fourier transform infrared (FTIR) spectroscopy showed no structural changes in Cur. Scanning electron microscopy (SEM) showed that Cur nanoparticles were uniformly spherical in shape. Differential scanning calorimetry (DSC) analysis showed a decrease in the crystallinity of the nanoparticles. Cur nanoparticles exhibited excellent membrane permeability in vitro, and the permeation rate in the first two hours was 25 folds higher than that of free Cur. Furthermore, Cur nanoparticles exhibited good transmembrane capacity in rabbits and significantly enhanced the bioavailability of Cur. The preparation of Cur nanoparticles using subcritical water method has the advantages of high drug loading, good membrane permeability, no need for carriers, simple process, and green environmental protection

Selective Catalytic Dehydrogenative Oxidation of Bio-Polyols to Lactic Acid

The global demand for lactic acid (LA) is increasing due to its successful application as monomer for the manufacture of bioplastics. Although N-heterocyclic carbene (NHC) iridium complexes are promising molecular catalysts for LA synthesis, their instabilities have hindered their utilization especially in commercial applications. Here, we report that a porous self-supported NHC-iridium coordination polymer can efficiently prevent the clusterization of corresponding NHC-Ir molecules and can function as a solid molecular recyclable catalyst for dehydrogenation of bio-polyols to form LA with excellent activity (97 %) and selectivity (>99 %). A turnover number of up to 5700 could be achieved in a single batch, due to the synergistic participation of the Ba2+ and hydroxide ions, as well as the blockage of unwanted pathways by adding methanol. Our findings demonstrate a potential route for the industrial production of LA from cheap and abundant bio-polyols, including sorbitol

A Journey into the City. Migrant Workers' Relation with the Urban Space and Struggle for Existence in Xu Zechen's Early Jingpiao Fiction

In contemporary China, rural-urban migrants constitute a new urban subject with entirely new identity-related issues. This study aims at demonstrating how literature can be a valid field in investigating such evolving subjectivities, through an analysis of Xu Zechen’s early novellas depicting migrants’ vicissitudes in Beijing. Combining a close reading of the texts and a review of the main social problems characterising rural-urban migration in China, this paper focuses on the representation of the identity crisis within the migrant self in Xu’s stories, taking into account the network of meanings employed by the writer to signify the objective and subjective tension between the city and the countryside

Highly efficient NHC-iridium-catalyzed β-methylation of alcohols with methanol at low catalyst loadings

The methylation of alcohols is of great importance since a broad number of bioactive and pharmaceutical alcohols contain methyl groups. Here, a highly efficient β-methylation of primary and secondary alcohols with methanol has been achieved by using bis-N-heterocyclic carbene iridium (bis-NHC-Ir) complexes. Broad substrate scope and up to quantitative yields were achieved at low catalyst loadings with only hydrogen and water as by-products. The protocol was readily extended to the β-alkylation of alcohols with several primary alcohols. Control experiments, along with DFT calculations and crystallographic studies, revealed that the ligand effect is critical to their excellent catalytic performance, shedding light on more challenging Guerbet reactions with simple alcohols

Numerical Investigation and Prediction of Side-By-Side Tunneling Effects on Buried Pipelines

With the fast development of underground space engineering, it is inevitable for buried pipelines to be crossed by twin tunnels. Previous studies mainly focused on the single-tunneling effects on pipelines. To emphasize the twin-tunneling effects on buried pipelines, we first examined the effectiveness of the ground settlement prediction method under twin-tunneling conditions. Then, the estimated ground settlement boundary condition was applied to the beam-on-spring finite element model. The numerical results show that with the decrease in tunnel depth and twin tunnel space, the values and positions of the maximum ground settlement and longitudinal pipe bending behavior both changed significantly. The biased distance of the maximum settlement position and the distance to the inflection point of the final ground settlement curve can be obtained by curve fitting. Based on that, a semi-empirical prediction method for the longitudinal pipe bending strain was proposed. The predicted values matched quite well with the numerical results, which can thus provide a quick and effective structural safety and integrity assessment approach for buried pipelines subjected to twin-tunneling conditions