Bio-Degradable Polyesters with Rigid Cyclic Diester from Camphor and Tartaric Acid.

Despite their excellent, useful, and stable properties, thermoplastics are constantly subject to environmental risks because of their low degradability under thermal, chemical, and mechanical stresses. To overcome the aforementioned issues, we hereby introduce an eco-friendly camphor (Ct) cyclic diester. The Ct diester is designed as a monomer, including a ketal group from the Ct, and shows high thermal stability via a rigid spiro-ring and a bridged bicyclic structure. A series of polyester was synthesized using the Ct diester, including various types of diols and dimethyl terephthalate. PETxCty copolyesters showed appropriate thermal stability up to 414 °C and a high glass transition temperature. This thermal behavior led to amorphous regions as the Ct diester content increased. Regarding the proportion of the Ct diester in the polyester, it was sensitive to hydrolysis and contributed to the degradation of the polyester in acid buffer conditions.

Influence of UV Polymerization Curing Conditions on Performance of Acrylic Pressure Sensitive Adhesives.

Acrylic pressure sensitive adhesives (PSAs) were prepared by UV polymerization under varying curing conditions of both fast and slow curing, employing high- and low-intensity UV radiation, respectively. The influences of curing conditions and isobornyl acrylate (IBOA) content on PSA performance were comprehensively investigated by measurement of their rheological, thermal, and adhesive properties. In particular, rheological characterization was accomplished by several analytical methods, such as in situ UV rheology, frequency sweep, stress relaxation, and temperature ramp tests, to understand the effect of the UV curing process and IBOA content on the viscoelastic behavior of acrylic PSAs. The slow-cured samples were observed to form more tightly crosslinked networks compared to the fast-cured. On the other hand, at high loading levels of IBOA, in the case of slow curing, the sample exhibited a contrasting trend, having the shortest stress relaxation time and the highest energy dissipation; this was due to molecular chain scission occurring in the crosslinked polymer during UV polymerization. Consequently, we successfully demonstrated the influence of monomer composition of acrylic PSAs, and that of curing conditions employed in UV polymerization. This study provides valuable insights for the development of crosslinked polymer networks of acrylic PSAs for flexible display applications.

A vacancy-driven phase transition in MoX2 (X: S, Se and Te) nanoscrolls.

Atomically thin MoX2 (MoS2, MoSe2 and MoTe2) exhibits semiconducting, metallic, and semi-metallic properties associated with different polymorphic phases such as 2H, 1T and distorted 1T (1T'), respectively. The phase transitions from 2H to 1T for TMDs have been reported, but the mechanism for the formation and fraction control of 1T and 1T' phases in phase transition processes has never been reported because the 1T and 1T' phases are very unstable even at room temperature. To solve the problem of the thermal instability in the 1T and 1T' phases and investigate the mechanism, we design and synthesize nanoscrolls of MoX2 which have two key attributes, bending strain for phase transition and van der Waals forces as the self-stabilizing energy for thermal stability at high temperature and then investigate the mechanism of phase transition in the synthesized nanoscrolls by an increase in temperature. It turns out that the phase transition of the 2H to the 1T phase is driven by the transition metal Mo vacancy in the XY plane and that of the 1T to the 1T' phase is induced by the chalcogen X vacancy in the Z plane. In addition, each phase itself and fractions of the 2H, 1T and 1T' phases in nanoscrolls can be freely controlled by inducing vacancies of transition metal and chalcogen with increasing temperature.

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10-3 S cm-1) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g-1 at 0.1 A g-1), better rate capability (64% capacity retention until 20 A g-1), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg-1 at 1 A g-1) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Fast Hydrolysis Polyesters with a Rigid Cyclic Diol from Camphor.

2,2:3,3-Bis(4'-hydroxymethylethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane, abbreviated as CaG, is a compound obtained by transforming a ketone group to a ketal group with camphorquinone and glycerol. The CaG diol has a complex and rigid structure and two primary hydroxyl groups. A polyester series was synthesized with the CaG diol, ethylene glycol, and dimethyl terephthalate. The polyesters exhibited adequate thermal stability up to nearly 330 °C and had a high Tg, which steadily increased from 78 to 129 °C as the content of CaG increased. A high proportion of the CaG moiety led to an amorphous region that is susceptible to hydrolysis and promoted degradation of the polyester in acidic conditions. Depending on the proportion of CaG in the polymer, the hydrolytic degradation of the polyesters was adjustable.

Highly efficient hydrogen evolution reaction by strain and phase engineering in composites of Pt and MoS2 nano-scrolls.

The phase transition through local strain engineering is an exciting avenue for controlling electronic, magnetic properties and catalyst activity of materials but complex phenomenon in nanoscience. Herein, we demonstrate the first combinations of bending strain and 2H/1T phase transition by rolling up MoS2 sheets for improving catalytic activity in relatively inert basal plane surfaces and promoting electron transfer from the less-conducting 2H MoS2 sheets to the electrodes. Furthermore, we generate various MoS2@Pt nanoparticle hybrids nanomaterials and especially MoS2@Pt scrolls containing the coverage of Pt NPs (8.3 wt%) have a high catalytic activity (39 mV per decade). The rolled up MoS2@Pt sheets with bending strain (2.4%) provide an intra-layer plane gliding that allows the transversal displacement of an S plane from the 2H to the 1T phases (28%). This unique combination also allows us to maximize the intrinsic HER activity among molybdenum-sulfide based catalysts.

Evolution of magnetism by rolling up hexagonal boron nitride nanosheets tailored with superparamagnetic nanoparticles.

Controlling tunable properties by rolling up two dimensional nanomaterials is an exciting avenue for tailoring the electronic and magnetic properties of materials at the nanoscale. We demonstrate the tailoring of a magnetic nanocomposite through hybridization with magnetic nanomaterials using hexagonal boron nitride (h-BN) templates as an effective way to evolve magnetism for the first time. Boron nitride nanosheets exhibited their typical diamagnetism, but rolled-up boron nitride sheets (called nanoscrolls) clearly have para-magnetism in the case of magnetic susceptibility. Additionally, the Fe3O4 NP sample shows a maximum ZFC curve at about 103 K, which indicates well dispersed superparamagnetic nanoparticles. The ZFC curve for the h-BN-Fe3O4 NP scrolls exhibited an apparent rounded maximum blocking temperature at 192 K compared to the Fe3O4 NPs, leading to a dramatic increase in TB. These magnetic nanoscroll derivatives are remarkable materials and should be suitable for high-performance composites and nano-, medical- and electromechanical-devices.

Highly thermal-stable paramagnetism by rolling up MoS2 nanosheets.

Controlling phase transitions through local strain engineering is an exciting avenue for tailoring the electronic and magnetic properties of materials at the nanoscale. Herein, we demonstrate a tunable semiconducting to metallic phase transition of two-dimensional transition metal dichalcogenides using strain engineering through rolled up MoS2 sheets (named as MoS2 scrolls). A phase incorporated structure for MoS2 nanoscrolls containing the maximum concentration of 1T phase (∼58%) with high thermal stability up to 473 K can be produced by a gliding-rolling process for the S plane. These phase transitions are irreversible by virtue of the van der Waals interaction between the layers of the nanoscrolls, which is relatively stronger than the bending strain. A high concentration of the 1T phase can tune the bandgap through temperature, and also the magnetic property from nonmagnetic to paramagnetic MoS2. This study, which is able to control phase transitions by strain engineering in the field of 2D materials, proves an exciting avenue for tailoring the novel functional properties of low-dimensional materials.

Evolution of a high local strain in rolling up MoS2 sheets decorated with Ag and Au nanoparticles for surface-enhanced Raman scattering.

We report that a high local strain was obtained for multilayer MoS2 nanoscrolls decorated with noble nanoparticles (Ag and Au NPs) using a rolling process beyond breaking or slipping of MoS2. The local strain was estimated through the bending strain in the nanoscrolls and the extent of coverage of Ag and Au NPs decorated on MoS2, exhibiting magnified surface-enhanced Raman scattering. TEM images showed that the MoS2-Ag and MoS2-Au nanoscrolls have a tube-like morphology decorated with NPs on the inner and outer sides of the MoS2 nanoscrolls. In the Raman spectra, we confirmed the red shift and broadness of the FWHM for nanoscrolls in the eigenvectors of the [Formula: see text] and [Formula: see text] modes. From the Grüneisen parameter γ and the shear deformation potential ß, we obtained peak shifts of ∼4.9 cm-1/% at [Formula: see text] and ∼1.1 cm-1/% strain at [Formula: see text] for free-standing MoS2. According to the obtained relationship of the Raman shift and the induced uniaxial tensile strain, the [Formula: see text] and [Formula: see text] peaks shifted upwards to around -12.8 cm-1 and -2.9 cm-1, respectively, and can be converted to an induced uniaxial tensile strain of about 2.6% for MoS2-Ag nanoscrolls.

Solution Processed Organic Photovoltaic Cells Using D-A-D-A-D Type Small Molecular Donor Materials with Benzodithiophene and Diketopyrrolopyrrole Units.

Organic photovoltaic Cells (OPVs) have been considered to be a next-generation energy source to overcome exhaustion of resources. Currently, OPVs are developed based on two types of donor material with polymer and small molecule. Polymeric donor materials have shown better power conversion efficiency (PCE) than small molecular donor materials, since it's easy to control the morphology of photoactive film. However, the difficulty in synthetic reproducibility and purification of polymeric donor were main drawback to overcome. And then, recently small molecule donor materials have been overcome bad morphology of OPVs film by using appropriate alkyl substituents and relatively long conjugation system. In this study, we designed and synthesized D-A-D-A-D type small molecular donor materials containing alternatively linked benzodithiophene (BDT) and diketopyrrolopyrrole (DPP) units. Also, we studied on the effect of photovoltaic performance of prepared small molecular D-A-D-A-D type donor with variation of thiophene links and with/without hexyl substituent. Our small molecular donors showed HOMO energy levels from -5.26 to -5.34 eV and optical bandgaps from 1.70 to 1.87 eV by CV (cyclic voltammetry) and UV/Vis spectroscopy, respectively. Finally, 3.4% of PCE can be obtained using a mixture of BDT(DPP)2-T2 and PCBM as an active layer with a Voc of 0.78 V, a Jsc of 9.72 mA/cm2, and a fill factor of 0.44 under 100 mW/cm2 AM 1.5G simulated light. We will discuss the performance of D-A-D-A-D type small molecular donor based OPVs with variation of both terminal substituents.

Formation of hexagonal boron nitride nanoscrolls induced by inclusion and exclusion of self-assembling molecules in solution process.

Unlike nanoscrolls of 2D graphene, those of 2D h-BN have not been demonstrated, except for only a few experimental reports. Nanoscrolls of h-BN with high yields and reproducibility are first synthesized by a simple solution process. Inner-tube diameters of BNSs including LCAs, N-(2-aminoethyl)-3α-hydroxy-5ß-cholan-24-amide, a bile acid derivative and self-assembling material, can be controlled by adjusting the diameter of the LCA fiber which is grown by self-assembly. TEM and SEM images show that BNSs have a tube-like morphology and the inner-tube diameter of BNSs can be controlled in the range from 20 to 60 nm for a smaller diameter, up to 300 nm for a larger diameter by LCA fiber growth inside the BNSs. Finally, open cylindrical BNSs with hollow cores were obtained by dissolving LCAs inside BNSs.

Patterned immobilization of biomolecules on a polymer surface functionalized by radiation grafting.

Patterned graft polymerization of a functional monomer on a hydrophobic polymer surface was proposed for biomolecule patterning. A poly(vinylidene fluoride) (PVDF) film surface was selectively activated by ion implantation through a pattern mask and acrylic acid (AA) was then graft polymerized onto the activated regions of the PVDF surfaces. The peroxide concentration on the implanted surface depended on the fluence, which had a considerable effect on the grafting degree of AA. Afterwards, amine-functionalized biotin and probe DNA were immobilized on the poly(acrylic acid)-grafted regions of the PVDF surfaces. Specific binding of biotin with streptavidin and hybridization of probe DNA with complimentary DNA proved successful protein and DNA patterning and well-defined 50 microm dot-type patterns of the streptavidin and DNA were obtained. These results confirmed the potential of this strategy for patterning of various biomolecules.

Functionalization of carbon nanotubes by radiation-induced graft polymerization.

Multi-walled carbon nanotubes (MWCNTs) were functionalized by radiation-induced graft polymerization of acrylic acid onto the surface of MWCNTs in order to improve their dispersibility in water. 1H NMR, Raman spectroscopy, TEM, and TGA techniques were used to characterize the resulting functionalized MWCNTs. The grafting degree was dependent on the grafting conditions such as the absorbed dose and the monomer concentration. The experimental results confirmed that poly(acrylic acid) chains were successfully grafted onto the surface of the MWCNTs. The poly(acrylic acid)-grafted MWCNTs showed a much better water dispersibility than the pristine MWCNTs.