Non-contact biomimetic mechanism for selective hydrogenation of nitroaromatics on heterogeneous metal nanocatalysts

While the enzymatic reduction of unsaturated compounds usually has high specificity,highly selective reduction processes are hardly realized by heterogeneous industrial catalysts,which is critical for the green production of many fine chemicals.Here,we report an unexpected discovery of a biomimetic behavior of dicyandiamide(DICY)-modified Pt nanocatalysts for the green hydrogenation of a wide range of nitroaromatics.We demonstrate that the surface modification by DICY not only prevents the direct contact of nitroaromatic reactants with Pt surface but also induces an effective non-contact hydrogenation mechanism mediated by protons and electrons.In such a process,the DICY layer serves as a“semi-permeable membrane”to allow the permeation of H_(2) molecules for being activated into electrons and protons at the Pt-DICY interface.With the generation of separated protons and electrons,the nitro group with strong electrophilic properties can be hydrogenated through the electron transfer followed by the proton transfer,which is facilitated by the hydrogen bonding network formed by protonated DICY.The unique mechanism makes it highly directional toward the hydrogenation of nitro groups without side reactions.Owing to its capability to largely eliminate the waste generation,the developed Pt-DICY catalysts have been successfully applied for the green industrial production of many important aniline intermediates.

Mechanics Unloading Analysis and Experimentation of a New Type of Parallel Biomimetic Shoulder Complex

The structure design for high ratio of carrying capacity to deadweight is one of the challenges for the bionic mechanism,while the problem concerning high carrying capacity has not yet be solved for the existing shoulder complex.A new type biomimetic shoulder complex,which adopts 3-PSS/S（P for prismatic pair,S for spherical pair） spherical parallel mechanism（SPM）,is proposed.The static equilibrium equations of each component are established by using the vector method and the equations for constrain forces with certain load are solved.Then the constrain force on the middle limb and that on the side limbs are compared in order to verify the unloading performance of the mechanism.In addition,the prototype mechanism of the shoulder complex is developed,and the force feedback experiment is conducted to verify the static analysis,which indicates that the middle limb suffers most of the external force and the effect of mechanics unloading is achieved.The 3-PSS/S spherical parallel mechanism is presented for the shoulder complex,and the realization of mechanics unloading is benefit for the improvement of the carrying capacity of the shoulder complex.

A bionic controllable strain membrane for cell stretching at air–liquid interface inspired by papercutting

Lung diseases associated with alveoli,such as acute respiratory distress syndrome,have posed a long-term threat to human health.However,an in vitro model capable of simulating different deformations of the alveoli and a suitable material for mimicking basement membrane are currently lacking.Here,we present an innovative biomimetic controllable strain membrane(BCSM)at an air–liquid interface(ALI)to reconstruct alveolar respiration.The BCSM consists of a high-precision three-dimensional printing melt-electrowritten polycaprolactone(PCL)mesh,coated with a hydrogel substrate—to simulate the important functions(such as stiffness,porosity,wettability,and ALI)of alveolar microenvironments,and seeded pulmonary epithelial cells and vascular endothelial cells on either side,respectively.Inspired by papercutting,the BCSM was fabricated in the plane while it operated in three dimensions.A series of the topological structure of the BCSM was designed to control various local-area strain,mimicking alveolar varied deformation.Lopinavir/ritonavir could reduce Lamin A expression under over-stretch condition,which might be effective in preventing ventilator-induced lung injury.The biomimetic lung-unit model with BCSM has broader application prospects in alveoli-related research in the future,such as in drug toxicology and metabolism.

Extracellular magnetic labeling of biomimetic hydrogel-induced human mesenchymal stem cell spheroids with ferumoxytol for MRI tracking

Labeling of mesenchymal stem cells(MSCs)with superparamagnetic iron oxide nanoparticles(SPIONs)has emerged as a potential method for magnetic resonance imaging(MRI)tracking of transplanted cells in tissue repair studies and clinical trials.Labeling of MSCs using clinically approved SPIONs(ferumoxytol)requires the use of transfection reagents or magnetic field,which largely limits their clinical application.To overcome this obstacle,we established a novel and highly effective method for magnetic labeling of MSC spheroids using ferumoxytol.Unlike conventional methods,ferumoxytol labeling was done in the formation of a mechanically tunable biomimetic hydrogel-induced MSC spheroids.Moreover,the labeled MSC spheroids exhibited strong MRI T2 signals and good biosafety.Strikingly,the encapsulated ferumoxytol was localized in the extracellular matrix(ECM)of the spheroids instead of the cytoplasm,minimizing the cytotoxicity of ferumoxytol and maintaining the viability and stemness properties of biomimetic hydrogel-induced MSC spheroids.This demonstrates the potential of this method for post-transplantation MRI tracking in the clinic.

Controlling the gelation temperature of biomimetic polyisocyanides

Thermosensitive polymers show an entropy-driven transition from a well-solvated to a poorly solvated polymer chain, resulting in a more compact globular conformation. The transition at the lower critical solution temperature（LCST） is often sharp, which allows for a wide range of smart material applications.At the LCST, oligo（ethylene glycol）-substituted polyisocyanides（PICs） form soft hydrogels, composed of polymer bundles similar to biological gels, such as actin, fibrin and intermediate filaments. Here, we show that the LCST of PICs strongly depends linearly on the length of the ethylene glycol（EG） tails; every EG group increases the LCSTand thus the gelation temperature by nearly 30 ℃. Using a copolymerisation approach, we demonstrate that we can precisely tailor the gelation temperature between 10 ℃ and 60 ℃and, consequently, tune the mechanical properties of the PIC gels.

Synthesis of Asymmetrical Monobenzo-Substituted Cobalt Thioporphyrazines and Their Biomimetic Catalytic Property

Two novel monobenzo porphyrazines bearing nitro and methoxyl respectively on fused benzene ring were suc- cessfully synthesized. Also, an asymmetrical porphyrazine with one butylthio branch at the pyrrolic p-position sub- stituted by hydrogen atom was successfully isolated in the course of synthesis of symmetric octakis（butylthio） porphyrazine. Their corresponding cobalt complexes were subsequently obtained and characterized. Their catalytic ability was assessed by aerobic oxidation of benzoin, showing the highest benzil yield of 95.2% for 60 min. A pos- sible mechanism was also presented from the in-situ UV-Vis spectra, in which a novel and characteristic absorption peak of metal-oxo was observed. At the same time, similar results of the extended oxidation of benzyl alcohol also confirmed the reactive mechanism.