Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation

Various cellulose II samples, ball-milled native celluloses and ball-milled wood saw dust were subjected to 2,2,6,6-tetramethypyperidine-1-oxyl radical (TEMPO)-mediated oxidation to prepare cellouronic acid Na salts (CUAs). The TEMPO-oxidized products obtained were analyzed by ¹³C-NMR and size-exclusion chromatography (SEC). When the cellulose II samples with degrees of polymerization (DP) of 220–680 were used as the starting materials, the CUAs obtained had weight-average DP (DPw) values of only 38–79. Thus, significant depolymerization occurs on cellulose chains during the TEMPO-mediated oxidation. These DP values of CUAs correspond to the cellulose II crystal sizes along the chain direction in the original cellulose II samples, but not necessarily to their leveling-off DP values. CUAs can be obtained also from ball-milled native celluloses in good yields by TEMPO-mediated oxidation, although their DPw values are lower than about 80. On the other hand, CUA with DPw of about 170 was obtained from ball-milled wood saw dust.     

Pressure generation at the junction of two microchannels with different depths

In this study, we report the design of a microchip‐based hydraulic pump that comprises three glass conduits arranged in a T‐geometry, one of which has a 2 mm long segment shallower (0.5–3 μm in depth) than the remaining 15 μm deep microfluidic network. Upon application of an electric field across this microchannel junction, a mismatch in EOF rate is introduced due to a differential in the fluid conductivity across the deep and shallow segments. Using the reported micropump, pressure‐driven velocities up to 3.2 mm/s have been generated in a 15 μm deep separation channel for an applied voltage of 1.75 kV allowing us to operate under separation conditions that yield the minimum plate height. Moreover, we have shown that this flow velocity can be maximized by optimizing the depth in the shallow region of the T‐geometry. Interestingly however, a simple theory accounting for fluid conductivity differences across microchannels of different depths significantly underestimates the pressure‐driven velocities observed in our experiments. The Taylor dispersion coefficient in our system on the other hand compares well with the theoretical predictions reported in the literature. Finally, the functionality of our device has been demonstrated by implementing a reverse‐phase chromatographic separation that was driven by the pressure‐driven flow generated on‐chip.     

Blending to Make Nonhealable Polymers Healable: Nanophase Separation Observed by CP/MAS 13C NMR Analysis

Can commodity polymers are made to be healable just by blending with self-healable polymers? Here we report the first study on the fundamental aspect of this practically challenging issue. Poly(ether thiourea) (PTUEG₃; T_g=27 °C) reported in 2018 is extraordinary in that it is mechanically robust but can self-heal even at 12 °C. In contrast, poly(octamethylene thiourea) (PTUC₈; T_g=50 °C), an analogue of PTUEG₃, cannot heal below 92 °C. We found that their polymer blend self-healed in a temperature range above 32 °C even when its PTUEG₃ content was only 20 mol %. Unlike PTUEG₃ alone, this polymer blend, upon exposure to high humidity, barely plasticized, keeping its excellent mechanical properties due to the non-hygroscopic nature of the PTUC₈ component. CP/MAS ¹³C NMR analysis revealed that the polymer blend was nanophase-separated, which possibly accounts for why such a small amount of PTUEG₃ provided the polymer blend with humidity-tolerant self-healable properties.     

Quadrupolar susceptibility and magnetic phase diagram of PrNi2Cd20 with non-Kramers doublet ground state

ABSTRACT

In this study, ultrasonic measurements were performed on a single crystal of cubic PrNi₂Cd₂₀, down to a temperature of 0.02?K, to investigate the crystalline electric field ground state and search for possible phase transitions at low temperatures. The elastic constant (C₁₁?C₁₂)/2, which is related to the Γ₃-symmetry quadrupolar response, exhibits the Curie-type softening at temperatures below ～30?K, which indicates that the present system has a Γ₃ non-Kramers doublet ground state. A leveling-off of the elastic response appears below ～0.1?K toward the lowest temperatures, which implies the presence of level splitting owing to a long-range order in a finite-volume fraction associated with Γ₃-symmetry multipoles. A magnetic field–temperature phase diagram of the present compound is constructed up to 28?T for H || [110]. A clear acoustic de Haas–van Alphen signal and a possible magnetic-field-induced phase transition at H ～26?T are also detected by high-magnetic-field measurements.     

Structural-transformation-induced Drastic Luminescence Changes in an Organic-Inorganic Hybrid [ReN(CN)4]2− Salt Triggered by Chemical Stimuli

We synthesized a (1-propylpyridinium)₂[ReN(CN)₄]-type organic–inorganic hybrid exhibiting water-vapor-induced drastic structural changes of the [ReN(CN)₄]²⁻ assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido-bridged chains were converted to hydrated cyanido-bridged tetranuclear clusters via rearrangements of large molecular building units in the crystals. These switchable assembly forms display substantially different photo-physical properties, although in both cases the emission is caused by a metal-centered d–d transition. The nitrido-bridged chain exhibited a near-infrared (749 nm) emission, which blue-shifted as the temperature increased, while a visible (561 nm) emission and its red shift was demonstrated by the cyanido-bridged cluster.     

Quantum feedback control for deterministic entangled photon generation

We present quantum feedback control for deterministic entanglement generation at the single-photon level. The protocol of controlling both total photon number and phase difference is based on the cascade structure of cavities placed in an optical closed loop, quantum nondemolition measurement with cross-Kerr interactions, and Lyapunov stability for feedback design.