Relative contributions of different sources to DOM in Erhai Lake as revealed by PLS-PM.

Dissolved organic matter (DOM) is a complex mixture of organic molecules that plays an important role in freshwater lake ecosystems. Excitation emission matrix-parallel factor analysis (EEM-PARAFAC) is an important tool for the identification and source analysis of DOM but is still inadequate for studying the differences and quantifying the contributions of different sources. Here, based on the maximum fluorescence intensities (Fmax) of the four fluorescent components (e.g., protein-like component C1, and the humic-like components C2, C3, C4) identified by EEM-PARAFAC, combined with large-scale data obtained from observations at Erhai Lake, we used partial least squares path modeling (PLS-PM) to improve the understanding of the migration and transformation mechanisms of DOM. The results showed that the phytoplankton and trophic state had greater impacts on DOM, while the impacts of sediment and inflow rivers were less significant. The results of the models that used nitrogen nutrients (N) and phosphorus nutrients (P) to separately indicate the trophic state suggested that the driving force of P on DOM was stronger than that of N in Erhai Lake. Among the four fluorescent components, the protein-like component with the largest relative proportion (41.98%) was mainly affected by phytoplankton, which was consistent with the autogenic characteristics obtained through spontaneous source index (BIX). The duality of the humic-like components was consistent with the duality of DOM through fluorescent index (FI). C3 had a higher sensitivity to the trophic state than the other components, and C2 received the greatest positive contribution from the rivers entering the lake. These results provide an improved insight into the influence of different sources on the behavior of DOM and demonstrate the potential of using PLS-PM to study the complex driving mechanism of aquatic biogeochemical parameters.

A class of organic cages featuring twin cavities.

A variety of organic cages with different geometries have been developed during the last decade, most of them exhibiting a single cavity. In contrast, the number of organic cages featuring a pair of cavities remains scarce. These structures may pave the way towards novel porous materials with emergent properties and functions.We herein report on rational design of a three-dimensional hexaformyl precursor 1, which exhibits two types of conformers, i.e. Conformer-1 and -2, with different cleft positions and sizes. Aided by molecular dynamics simulations, we select two triamino conformation capturers (denoted CC). Small-sized CC-1 selectively capture Conformer-1 by matching its cleft size, while the large-sized CC-2 is able to match and capture both conformers. This strategy allows the formation of three compounds with twin cavities, which we coin diphane. The self-assembly of diphane units results in superstructures with tunable proton conductivity, which reaches up to 1.37×10-5 S cm-1.

Diiodomethane-Mediated Generation of N-Aryliminium Ions and Subsequent [4 + 2] Cycloadditions with Olefins.

Herein, we report a method for in situ generation of N-aryliminium ions via reactions of N,N-dimethylanilines with diiodomethane. We used the method to prepare tetrahydroquinolines via one-pot three-component reactions between N,N-dimethylanilines, diiodomethane, and olefins. This transformation involves initial reaction of the aniline with diiodomethane to form an iodomethylammonium salt, which undergoes fragmentation accompanied by elimination of methyl iodide to give an N-aryliminium ion, which is trapped by the olefin via [4 + 2] cycloaddition to give the final product. This method for generating N-aryliminium ions requires neither a catalyst nor a strong oxidant, suggesting that it can be expected to find broad utility, especially for substrates that are sensitive to Lewis acids, transition metals, or strong oxidants.

C2 -Symmetric Bicyclic Bisborane Catalysts: Kinetic or Thermodynamic Products of a Reversible Hydroboration of Dienes.

We prepared a new class of chiral C2 -symmetric bicyclic bisborane catalysts by addition reactions of internal dienes with the Piers borane, HB(C6 F5 )2 , and an analogue, HB(p-C6 F4 H)2 . The dependence of the addition pattern on the reaction temperature allowed us to selectively prepare two diastereomeric catalysts from a single diene precursor. The bisboranes prepared in situ exhibited excellent activity (turnover numbers up to 200 at -40 °C) and enantioselectivity (up to 95 % ee) in imine hydrogenation reactions.

B(C6 F5 )3 -Catalyzed Ring Opening and Isomerization of Unactivated Cyclopropanes.

Catalytic amounts of B(C6 F5 )3 promote the ring opening and subsequent isomerization of a series of unactivated cyclopropanes to afford terminal olefins in good yields when a hydrosilane and 2,6-dibromopyridine are employed as additives.