Synthesis of Supramolecular A8 Bn Miktoarm Star Copolymers by Host-Guest Complexation.

We report a new synthetic method to construct supramolecular A8 Bn (n=1, 2, 4) miktoarm star copolymers by host-guest complexation between a resorcinarene-based coordination capsule possessing eight polystyrene chains and 4,4-diacetoxybiphenyl guest molecules that retain one, two or four polymethyl acrylate chains. The formation of the supramolecular A8 Bn (n=1, 2, 4) miktoarm star copolymers was confirmed by dynamic light scattering (DLS), size-exclusion chromatography (SEC), and diffusion-ordered NMR spectroscopy (DOSY). Differential scanning calorimetry (DSC) measurements revealed that the miktoarm copolymers were phase-separated in the bulk. The micro-Brownian motion of the A8 B4 structure was markedly enhanced in the bulk due to a weak segregation interaction between the immiscible arms.

Self-Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand-Based Coordination Capsules.

The repeating guest units of poly-(R)-2 were selectively encapsulated by the self-assembled capsule poly-1 possessing eight polymer side chains to form the supramolecular graft polymer (poly-1)n ⋅poly-(R)-2. The encapsulation of the guest units was confirmed by 1 H NMR spectroscopy and the DOSY technique. The hydrodynamic radius of the graft polymer structure was greatly increased upon the complexation of poly-1. The supramolecular graft polymer (poly-1)n ⋅poly-(R)-2 was stably formed in the 1:1 host-guest ratio, which increased the glass transition temperature by more than 10 °C compared to that of poly-1. AFM visualized that (poly-1)n ⋅poly-(R)-2 formed the networked structure on mica. The (poly-1)n ⋅poly-(R)-2 gelled in 1,1,2,2-tetrachloroethane, which led to fabrication of distinct viscoelastic materials that demonstrated self-healing behavior in a tensile test.

Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer.

The homopolymeric sequence formed by the head-to-head association of tetrakisporphyrin 1 is completely dissociated by the competitive association of the ditopic guest G2, resulting in the supramolecular copolymer poly-1⋅G2 with an alternatingly repeating host-guest sequence. The 1:1 stoichiometry of 1 and G2 is confirmed by a Job plot using UV/Vis titration and diffusion-ordered NMR spectroscopy (DOSY). The solution viscometry for poly-1 and poly-1⋅G2 suggests that the supramolecular chain of poly-1 behaves like a rod, whereas the supramolecular copolymer chain of poly-1⋅G2 behaves like a swelled fat chain, which is entangled in the semi-dilute regime. Atomic force microscopy shows that the supramolecular polymer poly-1⋅G2 is highly oriented through the interdigitation of the long alkyl chains.

Supramolecular Porphyrin Copolymer Assembled through Host-Guest Interactions and Metal-Ligand Coordination.

Bisporphyrin cleft molecule 1 Zn possessing a guest moiety assembled to form supramolecular polymers through host-guest interactions. Bispyridine cross-linkers created interchain connections among the supramolecular polymers to form networked polymers in solution. Solution viscometry confirmed that the cross-linked supramolecular polymers were highly entangled. Frequency-dependent linear viscoelastic spectroscopy revealed that the supramolecular polymers generated well-entangled solutions with associating and networking polymers, whereas the solid-like aggregates moved individually without breaking and reforming structures below the transition temperature of 9.6 °C. Morphological transition of the supramolecular polymers was evidenced by AFM images; the non-cross-linked polymer resulted in wide-spread thin networks, while the cross-linked networks produced thicker worm-like nanostructures. The supramolecular networks gelled in 1,1,2,2-tetrachloroethane, and an elastic free-standing film was fabricated with a Young's modulus of 1 GPa.

Real-Time Monitoring of Pellet Plastication in a Full-Flight Screw and Kneading Disk Elements of a Co-Rotating Self-Wiping Twin-Screw Extruder by Acoustic Emission (AE) Sensing.

The plastication of pellets in a co-rotating twin-screw extruder is a significant concern for product homogeneity and stability in the plastic industry. We developed a sensing technology for pellet plastication in a plastication and melting zone in a self-wiping co-rotating twin-screw extruder. The collapse of the solid part of the pellets emits an elastic wave as an acoustic emission (AE) that is measured on the kneading section of the twin-screw extruder using homo polypropylene pellets. The recorded power of the AE signal was used as an indicator of the molten volume fraction (MVF) in the range of zero (fully solid) to unity (fully melted). MVF decreased with increasing feed rate monotonically in the range of 2-9 kg/h at a screw rotation speed of 150 rotations per minute (rpm) because of the reduction in the residence time of pellets in the extruder. However, the increase in feed rate from 9 to 23 kg/h at 150 rpm resulted in an increase in the MVF as the friction and compaction of pellets caused their melting. The AE sensor could elucidate the pellet's plastication phenomena caused by friction, compaction of pellets, and melt removal in the twin-screw extruder.

Experimental and Numerical Simulation Study of Devolatilization in a Self-Wiping Corotating Parallel Twin-Screw Extruder.

Devolatilization is an important process for separating and removing unnecessary residual volatile substances or solvents during the production of polymers using twin-screw extruders. Latinen proposed a surface renewal model to determine the concentration of volatile components in the extrudate of a single-screw extruder. When a twin-screw extruder is used to calculate the concentration, it is necessary to use the exposed surface area of the resin in the starved region of Latinen's model, which, however, is difficult to estimate. In our previous work, we numerically determined resin profiles of the screws using the 2.5D Hele-Shaw flow model and the finite element method, which helps in estimating the surface area of devolatilization. In this study, we numerically analyzed the volatile concentration of the extrudate in a self-wiping corotating twin-screw extruder using Latinen's surface renewal model along with our resin profile calculation method. The experimental results of the concentrations of the volatile component (toluene) in the extrudate of polypropylene agreed well with its numerical calculation with a relative error of 6.5% (except for the data of the lowest rotational speed). Our results also showed that decreasing the flow rate and increasing the pump capacity were effective for removing the volatile component. The screw pitch of a full-flight screw was not affected by the devolatilization efficiency with a fixed flow rate and screw speed.

Facile Synthesis of an Eight-Armed Star-Shaped Polymer via Coordination-Driven Self-Assembly of a Four-Armed Cavitand.

The polystyrene chains were installed at the lower rim of a resorcinarene-based cavitand via reversible addition-fragmentation (RAFT) polymerization to form a four-armed star-shaped polymer. A star-shaped polystyrene-functionalized supramolecular capsule was prepared through the coordination-driven self-assembly of the four-armed start-shaped polymer with silver ions. The eight-armed start-shaped supramolecular capsule encapsulated 4,4'-diacetoxybiphenyl as did a cavitand-based self-assembled capsule. A DOSY measurement indicated that the eight-armed star-shaped polymer was twice as large as the four-armed star-shaped polymer. The solution behaviors of these compounds resulted in a difference in their zero-shear viscosities.

[Anesthetic management of four pediatric patients with CCAM for pulmonary lobectomy].

We report perioperative management of four pediatric patients with congenital cystic adenomatoid malformation (CCAM) for pulmonary lobectomy under general anesthesia combined with thoracic epidural anesthesia. The patients were two newborn infants and two infants. A 23-day-old girl whose cyst contained air and a one-day-old girl whose cyst content was drained percutaneously before induction, showed uneventful courses during perioperative period. In a one-yr-old boy with a cyst filled with purulent material, the endotracheal tube became nearly occluded with copious purulent material during operative period, and the management of this case was extremely difficult. After this case, in the other infant case expected to have purulent cyst as the result of repetitive infection, we inserted 5 Fr Fogaty catheter into the orifice of the left inferior bronchus to protect the normal side. This case showed uneventful course during anesthesia. We conclude that anesthesiologists should choose proper airway management method depending on the nature of cystic fluid in these patients.

The reduction in minimum alveolar concentration for tracheal extubation after clonidine premedication in children.

UNLABELLED: The effects of clonidine on minimum alveolar concentration for tracheal extubation (MAC-ex) have not been elucidated. Clonidine may lead to prolonged emergence from anesthesia. We investigated the effects of oral clonidine premedication on MAC-ex and examined the emergence properties of sevoflurane in children. Sixty ASA physical status I pediatric patients, aged from 2 to 9 yr, were randomly divided into one of three groups and received placebo, clonidine 2 microg/kg, or clonidine 4 microg/kg (n = 20 each) orally, 100 min before the induction of anesthesia. The induction of anesthesia, tracheal intubation, and maintenance of anesthesia were performed with sevoflurane in air and oxygen. MAC-ex was defined according to the modification of Dixon's up-and-down method, with 0.25% as a step size. In addition, in the Control and 4 microg/kg groups, the time from tracheal extubation to spontaneous eye opening (eye-opening time) and the time from tracheal extubation to leaving the operating room (awakening time) were recorded. MAC-ex for sevoflurane (mean +/- SD) was 1.63% +/- 0.13%, 1.04% +/- 0.26%, and 0.66% +/- 0.09% respectively in the Control group, 2 microg/kg group, and 4 microg/kg group. Significant differences were observed among the three groups. The eye-opening times were 5.7 +/- 3.5 min in the Control group and 5.1 +/- 1.0 min in the 4 microg/kg group. The awakening times were 9.7 +/- 3.7 min in the Control group and 9.2 +/- 3.8 min in the 4 microg/kg group. No significant differences were observed among the groups. IMPLICATIONS: Oral clonidine premedication decreased MAC for tracheal extubation for sevoflurane dose dependency and did not prolong emergence from anesthesia.

The hypnotic and analgesic effects of oral clonidine during sevoflurane anesthesia in children: a dose-response study.

UNLABELLED: Although clonidine has both hypnotic and analgesic actions, the dose relationship for each actions is still unknown in a clinical setting when clonidine is used as a premedication in children. We studied 80 ASA physical status I children (age range, 3-8 yr). Subjects were randomly divided into two groups (minimum alveolar anesthetic concentration [MAC]-Awake group, n = 40; MAC-Tetanus group, n = 40). Each patient received one dose of clonidine from 1 to 5 microg/kg orally, 100 min before arrival at the operating room. Anesthesia was induced and maintained with sevoflurane in oxygen and air. Before tracheal intubation, end-tidal sevoflurane was decreased stepwise by 0.2% at the start of 1.2%, a verbal command was given to the patients, and MAC-awake was determined in each patient. We also investigated MAC-tetanus, determined with transcutaneous electric tetanic stimulations, after tracheal intubation in each patient by observing the motor response to a transcutaneous electric tetanic stimulus to the ulnar nerve at a sevoflurane concentration decreased stepwise by 0.25% at the start of 2.75%. The initial reduction in MAC-tetanus was not as steep as that in MAC-awake. Clonidine reduced MAC-tetanus by 40% at the maximal dose of 5 microg/kg, whereas MAC-awake was already reduced by 50% at 2 microg/kg. We conclude that separate dose-response relationships for oral clonidine are present regarding the hypnotic and analgesic effects in children undergoing sevoflurane anesthesia. IMPLICATIONS: Separate dose-response relationships for oral clonidine were found regarding the hypnotic and analgesic effects in children undergoing sevoflurane anesthesia.

Sedation and plasma concentration of clonidine hydrochloride for pre-anesthetic medication in pediatric surgery.

Clonidine hydrochloride has been used for pre-anesthetic medication to provide a pre-operative sedation in pediatric surgery. The purpose of this study is to determine the plasma clonidine concentration, which gives satisfactory sedation in pediatric surgery. Sixteen pediatric patients (age: 1-11 years, weight: 9-33 kg) received either 2 or 4 microg/kg of clonidine lollipop before entering the operating room. Plasma clonidine concentrations were determined 120 min after administration of clonidine lollipop. Pre-operative sedation was evaluated by 5-point scoring systems at entering the operating room. The changes in systolic blood pressure (SBP), diastolic blood pressure (DBP) and heart rate (HR) were also assessed before and after administration of clonidine lollipop. The patients with satisfactory sedation had higher plasma clonidine concentration than that of the patients with unsatisfactory sedation (0.45+/-0.16 ng/ml vs. 0.26+/-0.16 ng/ml, p<0.05). The clonidine concentrations in the satisfactory group ranged from 0.28 to 0.81 ng/ml. There was no significant difference in hemodynamic parameters (SBP, DBP and HR) before and after administration of clonidine lollipop in both satisfactory and unsatisfactory sedation groups. Plasma clonidine concentration of 0.3-0.8 ng/ml would be sufficient to produce satisfactory sedation without changes in hemodynamic parameters in pediatric surgery.