Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

A microfluidics-dispensing-printing strategy for Janus photonic crystal microspheres towards smart patterned displays

From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe₃O₄ nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe₃O₄ hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays.     

Interface and defects engineering for multilayer laser coatings

High-reflective multilayer laser coatings are widely used in advanced optical systems from high power laser facilities to high precision metrology systems. However, the real interface quality and defects will significantly affect absorption/scattering losses and laser induced damage thresholds of multilayer coatings. With the recent advances in the control of coating design and deposition processes, these coating properties can be significantly improved when properly engineered the interface and defects. This paper reviews the recent progress in the physics of laser damage, optical losses and environmental stability involved in multilayer reflective coatings for high power nanosecond near-infrared lasers. We first provide an overview of the layer growth mechanisms, ways to control the microstructures and reduce layer roughness, as well as the nature of defects which are critical to the optical loss and laser induced damage. Then an overview of interface engineering based on the design of coating structure and the regulation of deposition materials reveals their ability to improve the laser induced damage threshold, reduce the backscattering, and realize the desirable properties of environmental stability and exceptional multifunctionality. Moreover, we describe the recent progress in the laser damage and scattering mechanism of nodule defects and give the approaches to suppress the defect-induced damage and scattering of the multilayer laser coatings. Finally, the present challenges and limitations of high-performance multilayer laser coatings are highlighted, along with the comments on likely trends in future.     

Helicate tris(aryl)carbinolates bearing pendant NR2 donors – a new family of supporting ligands for the synthesis of Sc3+ alkyl complexes

The reactions of aryllithium reagents o-LiC₆H₄CH₂NR₂ with (MeO)₂CO afford two new tris(aryl)carbinols bearing pendant-NR₂ donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C₆H₄CH₂NMe₂)₃CO]Sc(CH₂SiMe₃)₂ featuring rigid binding of the alkoxy anion through a κ¹-O, κ²-N chelating coordination mode     

One-pot,one-step,and selective terpolymerization of ethylene oxide,propylene oxide,and COS to copoly(thioether)s with tunable thermal properties

Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (T_m) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, T_m values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials.     

Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains

Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC_2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC_2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.     

Synthesis and crystal structures of novel glycoluril carboxylic acids conglomerates

The two novel conglomerates were obtained by crystallization of racemic (2'S,3aS,6aR)/(2'R,3aR,6aS) (glycoluril-1-yl)-3-methylbutanoic acid and (2'R,3aR,6aR)/(2'S,3aS,6aS) (4,6-dimethylglycoluril-1-yl)pentanoic acid synthesized by highly diastereoselective condensation of 4,5-dihydroxy- imidazolidin-2-ones with racemic ureido acids. The differences in the molecular geometry of synthesized racemates were studied by X-ray diffraction that showed them to crystallize as conglomerates in non-centrosymmetric space groups Pna2₁ and P2₁2₁2₁, respectively     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.