Schiff base modified starch: A promising biosupport for palladium in Suzuki cross-coupling reactions.

Starch can be used in diverse fields because it is a readily available, non-toxic polysaccharide with adaptable functionality and biodegradability. In this study, taking the aforementioned characteristics into consideration, we designed a modified starch (Starch-SB), which serves as supporting material for palladium stabilization. This new air and moisture-stable robust palladium composite [Starch-SB-Pd(II)] was characterized by FT-IR, XRD, TGA, XPS, SEM, EDX, TEM, CP/MAS 13C NMR, and ICP-MS analytical techniques. The catalytic studies exhibit high activity (up to 99 %) and stability in Suzuki cross-coupling reactions for this starch supported catalytic system under mild conditions (lower reaction temperature and green solvents) because of the cooperative interactions of multifunctional capturing sites on starch (Schiff base, hydroxy and amine groups) with palladium species. The experiments on reusability demonstrate that Starch-SB-Pd(II), which was prepared from functionalized starch, could be readily recycled several cycles through centrifugation. Moreover, we proposed a possibly multifunctional complex structure. This work presents an appealing and intriguing pathway for the utilization of polysaccharide as crucial support in green chemical transformations.

Ru-Pd Thermoresponsive Nanocatalyst Based on a Poly(ionic liquid) for Highly Efficient and Selectively Catalyzed Suzuki Coupling and Asymmetric Transfer Hydrogenation in the Aqueous Phase.

The development of intelligent polymeric materials to precisely control the catalytic sites of heterogeneous catalysts and enable highly efficient catalysis of a cascade reaction is of great significance. Here, the utilization of a polymer ionic liquid (PIL) containing two different anions facilitates the preparation of Ru-Pd catalysts with controllable phase transition temperatures and hydrophilic and hydrophobic surfaces. The combined multifunctionality, synergistic effects, micellar effects, aggregation effects, and temperature responsiveness of the nanocatalyst render it suitable for promoting selectively catalyzed Suzuki coupling and asymmetric transfer hydrogenation in water. Above the lower critical solution temperature (LCST) of the catalyst, it catalyzes only the coupling reaction with a high turnover number (TON) of up to 999.0. Below the LCST, the catalyst catalyzes only the asymmetric transfer hydrogenation with good catalytic activity and enantioselectivity. It is important that the catalyst can be simply and effectively recovered and recycled at least 10 times without significant loss of catalytic activity and enantioselectivity. This study also highlights the superiority of multifunctional heterogeneous catalysts based on PILs, which not only overcome limitations associated with low activity of heterogeneous catalysts but also realize selective reactions according to a temperature change, thereby improving the reactivity and enantioselectivity in multiple organic transformations.

Cu-Embedded SnSe2 with a High Figure of Merit at Ecofriendly Temperature.

There are many studies concentrated on high-temperature performance of SnSe2, but few studies were conducted on low-temperature properties of embedded SnSe2. In this work, a series of SnCu x Se2 (x = 0, 0.01, 0.02, and 0.05) layered structures have been successfully synthesized by a melt quenching, mechanical milling process, and spark plasma sintering (SPS) method. Meanwhile, the thermal and electrical transport properties of all synthesized samples are measured. These results suggest that the embedding of Cu into SnSe2 results in a high carrier concentration (1019/cm3). In addition, the enhancement of defect and interfacial phonon scattering caused by Cu embedding as well as the weak van der Waals force between layers makes a low thermal conductivity (0.81 W/mK) for the SnCu0.01Se2 at 300 K. Moreover, the maximum ZT is acquired up to 0.75 for the SnCu0.01Se2 sample at 300 K, which is about 2 orders of magnitude higher than the pristine sample (0.009). These features indicate that Cu-embedded SnSe2 can be a promising thermoelectric material at gentle temperature.

DFT-Calculated IR Spectrum Amide I, II, and III Band Contributions of N-Methylacetamide Fine Components.

The infrared spectrum (IR) characteristic peaks of amide I, amide II, and amide III bands are marked as amide or peptide characteristic peaks. Through the nuclear magnetic resonance study, N-methylacetamide has been determined to have six fine components, which include protonation, hydration, and hydroxy structures. Then the independent IR spectrum of every component in N-methylacetamide is calculated by using the density functional theory quantum chemistry method, and the contribution of each component to amide I, II, and III bands is analyzed. The results of this research can help to explain the formation of the amide infrared spectrum, which has positive significance in organic chemistry, analytical chemistry, and chemical biology.

Removal of aqueous Cr(VI) by a magnetic biochar derived from Melia azedarach wood.

Magnetic biochar (MMABC) prepared from Melia azedarach wood was used for aqueous Cr(VI) removal. MMABC was a mesoporous material with SBET 5.219 m2/g and superparamagnetic magnetization 17.3 emu/g contributed by the contained Fe3O4. The MMABC showed higher removal efficiency (99.8%) than biochar under conditions of dosage 5 g/L, pH = 3.0, and Cr(VI) concentration 10 mg/L. The saturation magnetization (16.1emg/g) of MMABC still remained after adsorption. According to FTIR and Raman results, the benzene-ring adjacent carbonyl did not showed obvious positive effects on Cr(VI) removal. A potential mechanism and corresponding apparent kinetic model indicated the Cr(VI) removal process by MMABC followed adsorption-reduction-adsorption steps. Cr(VI) was firstly adsorbed on surface and subsequently reduced to Cr(III), which was further adsorbed on MMABC surface. Langmuir isotherm (with maximal adsorption capacity of 25.27 mg/g) and pseudo second-order kinetic model were suitable for adsorption step.

Polymer ionic liquid network: a highly effective reusable catalyst for one-pot synthesis of heterocyclic compounds.

Significant efforts have been devoted to developing immobilized chiral catalysts with high activity, selectivity, and stability. In this present study, a new heterogeneous proline catalyst system was prepared based on strong noncovalent interactions between polymer ionic liquid (PIL) and l-proline. First, pyridine PILs, which can complex with l-proline monomers through noncovalent interactions, were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymer network-supported chiral catalysts were obtained following further free radical polymerization. Different structures were formed in response to different ratios of PIL and chiral monomer, as well as different PIL anions, in the reactions. The new formed layer structures and synergic effects of PIL resulted in heterogeneous catalysts with high catalytic activity and enantioselectivity, thus endowing them with better catalytic performance for the one-pot synthesis of heterocyclic compounds compared to homogeneous catalytic systems. These catalytic systems were able to be reused and recycled five times with no discernible loss in catalytic activity and enantioselectivity. l-Proline was efficiently loaded onto the polymer network simply based on supramolecular interactions, providing a novel method of synthesizing high performance supported catalysts for organic reactions.

Poly(Ionic Liquid) Based Chemosensors for Detection of Basic Amino Acids in Aqueous Medium.

Naked-eye detection of amino acids (AA) in water is of great significance in the field of bioanalytical applications. Herein, polymerized ionic liquids (PILs) with controlled chain length structures were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization and post-quaternization approach. The AA recognition performance of PILs with different alkyl chain lengths and molecular weights was evaluated by naked-eye color change and ultraviolet-visible (UV-vis) spectral studies. These PILs were successfully used for highly sensitive and selective detection of Arg, Lys, and His in water. The recognition performance was improved effectively with increased molecular weight of PILs. The biosensitivity of the PILs in water was strongly dependent on their aggregation effect and polarization effect. Highly sensitive and selective detection of AA was successfully accomplished by introducing positively charged pyridinium moieties and controlled RAFT radical polymerization.

Nanoparticle Based on Poly(Ionic Liquid) as an Efficient Solid Immobilization Catalyst for Aldol Reaction and Multicomponent Reaction in Water.

An environmentally friendly nanoparticle-supported catalyst was successfully prepared via in situ ionic complexation between imidazolium-based polymer ionic liquid (PIL) and poly(l-prolinamide-co-MAA). The physical and chemical properties of the obtained nanoparticles were characterized by TEM, FTIR, XPS, and static water contact angle experiments. The surface properties of the nanoparticle were found to significantly affect the catalytic performance. The nanoparticle with PIL outer facilitated the adsorption of reaction substrate in it. As a result, the catalytic system catalyzed the asymmetric Aldol reaction and multicomponent reaction in pure water efficiently. The catalytic system was able to be reused and recycled five times, and with no discernible loss in catalytic activity and enantioselectivity. These findings suggest that nanoparticles based on PIL may provide a new approach for preparing high performance supported catalysts for organic reactions in water. This technology also addresses issues associated with mass transfer in pure water reactions.