Hydrogels of chemically cross-linked and organ-metallic complexed interpenetrating PEG networks

The aim of the present work was to prepare a well-defined hydrogel of chemically cross-linked and organ-metallic complexed interpenetrating PEG networks. The hydrogel was synthesized via the reaction of copper(I)- catalyzed 1,3-dipolar azide-alkyne cycloaddition(CuA AC) with poly(ethylene glycol)-dopamine(PEG-DA)("Click Chemistry") followed by complexation with Fe~(3+) ions to crosslink the polymeric network. The chemical composition and morphology of the resulting hydrogels were characterized by Fourier transform infrared spectroscopy(FTIR), ~1H-NMR and scanning electron microscopy(SEM). Swelling ratio, mechanical strength, conductivity, and degradation behaviors of the hydrogels were also studied. The effect of the polymer chain length on properties of hydrogels was explored. The compressive strength of hydrogels could reach as high as 13.1 MPa with a conductivity of 2.2 × 10~(-5) S·cm~(-1). The hydrogels also exhibited excellent thermal stability even at a temperature of 300 °C, whereas degradation of the hydrogel after 7 weeks was observed under a physiological condition. In addition, the hydrogel exhibited a good biocompatibility based on its in vivo performance through an in vivo subcutaneous implantation model. No inflammation and no obvious abnormality of the surrounding tissue were observed when the hydrogel was subcutaneously implanted for 2 weeks. This work is a step towards creating a new pathway to synthesize hydrogels of interpenetrating networks which could be of important applications in the future research.     

Comparison of Py*+/dU*- charge transfer state dynamics in 5-(1-pyrenyl)-2'-deoxyuridine nucleoside conjugates with amido-, ethylenyl-, and ethynyl linkers

Femtosecond, picosecond, and nanosecond transient absorbance (TA) and picosecond emission kinetics results are presented for three 5-(1-pyrenyl)-2'-deoxyuridine nucleosides each with a different two-atom linker joining pyrenyl C-1 to uracil C-5. The linkers are respectively -NHCO-, -(CH(2))(2)-, and -C[triple bond]C- for PAdU, PEdU, and PYdU. For all three nucleoside conjugates, most conformers undergo intramolecular charge transfer (CT) from their pyrenyl (1)(pi,pi) excited states to form Py(*+)/dU(*-) CT products in ultrashort times: 相似文献   

Theoretical Study of the Substituent Effects on the Nonlinear Optical Properties of a Room‐Temperature‐Stable Organic Electride

Excess‐electron compounds can be considered as novel candidates for nonlinear optical (NLO) materials because of their large static first hyperpolarizabilities (β₀). A room‐temperature‐stable, excess‐electron compound, that is, the organic electride Na@(TriPip222), was successfully synthesized by the Dye group (J. Am. Chem. Soc. 2005 , 127, 12416). In this work, the β₀ of this electride was first evaluated to be 1.13×10⁶ au, which revealed its potential as a high‐performance NLO material. In particular, the substituent effects of different substituents on the structure, electride character, and NLO response of this electride were systemically studied for the first time by density functional theory calculations. The results revealed that the β₀ of Na@(TriPip222) could be further increased to 8.30×10⁶ au by introducing a fluoro substituent, whereas its NLO response completely disappeared if one nitryl group was introduced because the nitro‐group substitution deprived the material of its electride identity. Moreover, herein the dependence of the NLO properties on the number of substituents and their relative positions was also detected in multifluoro‐substituted Na@(TriPip222) compounds.     

Organocatalytic,Asymmetric Total Synthesis of (−)‐Haliclonin A

The first total synthesis of the alkaloid (−)‐haliclonin A is reported. The asymmetric synthesis relied on a novel organocatalytic asymmetric conjugate addition of nitromethane with 3‐alkenyl cyclohex‐2‐enone to set the stereochemistry of the all‐carbon quaternary stereogenic center. The synthesis also features a Pd‐promoted cyclization to form the 3‐azabicyclo[3,3,1]nonane core, a SmI₂‐mediated intermolecular reductive coupling of enone with aldehyde to form the requisite secondary chiral alcohol, ring‐closing alkene and alkyne metathesis reactions to build the two aza‐macrocyclic ring systems, and an unprecedented direct transformation of enol into enone.     

凹凸棒石负载Cu-Fe-Co基催化剂组合体系用于CO加氢制备低碳醇

采用浸渍法(IM)和浸渍燃烧法(IMSC)制备了凹凸棒石(ATP)及凹凸棒石-多孔硅胶微球混合物(ATPS)负载CuFe-Co基改性费托催化剂,通过N_2吸附-脱附、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)、H_2-程序升温还原(H_2-TPR)和CO_2-程序升温脱附(CO_2-TPD)等手段对催化剂进行了表征,并将它们应用于CO加氢制备低碳醇反应。结果表明,IMSC较IM制备催化剂更有利于CuO的负载、分散和还原,促进H_2和CO与Cu活性位的接触,但两者的最佳低碳醇合成温度均为280℃。通过对ATP和ATPS负载Cu-Fe-Co基催化剂(CFCK/ATP、CFCK/ATPS)与Cu/ZnO/Al_2O_3(CZA)甲醇催化剂的组合体系的优化,获得较理想的低碳醇合成催化剂组合体系CZA║CFCK/ATPS-IMSC。利用它们之间的"产物转化耦合效应",实现CO转化率为46.3%,低碳醇选择性为39.6%,C_(2+)醇含量为22.7%。     

An Intrinsic Photothermal Liquid for Light Detection and Energy Storage

Photothermal materials (PTMs) have been intensively investigated in the fields of photothermal conversion. Superior to solid PTMs, liquid PTMs are leading the trends in satisfying the demands of high flexibility and easy recycling. Successful examples of liquid PTMs are mostly formulated by dispersing solid PTMs in solvents, but suffer from the problems of phase segregation and solvent pollution. In this work, a low-cost formulation is proposed, which involves an oxidative product of ethyl oleate by iodine. It is an intrinsic liquid PTM, preserving the fluidic nature as well as possessing considerable ability for photothermal conversion. In addition to understanding the mechanism of light absorption in the visible and even near infrared windows, two examples are presented to demonstrate the great potential of liquid PTMs in broad areas such as light sensing and energy storage.     

Kinetic Monte Carlo simulations of nucleation and growth in electrodeposition

Nucleation and growth during bulk electrodeposition is studied using kinetic Monte Carlo (KMC) simulations. Ion transport in solution is modeled using Brownian dynamics, and the kinetics of nucleation and growth are dependent on the probabilities of metal-on-substrate and metal-on-metal deposition. Using this approach, we make no assumptions about the nucleation rate, island density, or island distribution. The influence of the attachment probabilities and concentration on the time-dependent island density and current transients is reported. Various models have been assessed by recovering the nucleation rate and island density from the current-time transients.     

A basket tetradecavanadate cluster with blue luminescence

A blue luminescent tetradecavanadate compound, [Et4N]5[V14O36Cl], has been synthesized. It possesses an unprecedented half-open basket framework. Through the {ABAB}-type stacking, the {V14O36} clusters form infinite one-dimensional channels with considerable accessible volume in the crystalline state.     

Photo-and Electro-luminescence of the New Ternary Europium(III) Complex

In recent years, the interest in developing luminescent lanthanide complexes has been greatly stimulated by their potential use in electroluminescent displays1. Europium complexes appear most attractive in view of the high photoluminescent efficiency and the high monochromatic red light that are widely exploited in full-color displays2. It has been approved that the second ligand plays an important role in europium complexes, the synergistic complexation of the second ligand can not only lead …     

The First Total Synthesis of Triprenylquinone and Hydroquinones

Marine natural products have received much attention for their attractive structural features and biological activities1. Since the isolation of the moritoside, about 10 related triprenylquinones and hydroquinones were isolated. Some of these natural products exhibit interesting biological effects including inhibit cell division of fertilized starfish eggs2 and anti-HIV3. Triprenylquinone and hydroquinones 1, 2 and 3 were recently isolated from endemic nudibranch Leminda millecra collected i…