Metastable liquid crystal as time-responsive reaction medium: aging-induced dual enantioselective control.

A metastable liquid crystal (LC) was found to serve as a time-responsive reaction medium, in which the enantioselectivity of a photoreaction was perfectly switched through isothermal annealing of the reaction system. When the LC salt of an enantiopure amine with a photoreactive acid was irradiated with UV/vis light, in situ photodimerization of the acid moiety proceeded smoothly to afford the (+)-isomer of the photodimer with high enantioselectivity (+86% ee). In contrast, photoirradiation of an aged sample, isothermally annealed for 20 h, gave predominantly the (-)-isomer (-94% ee). Systematic studies revealed that the reversal in selectivity originated from metastability of the LC system, which gradually transformed into a crystalline phase during annealing. This finding demonstrates the potential use of metastable aggregates as dynamic time-responsive media, reminiscent of biological systems.

Tunable chiral reaction media based on two-component liquid crystals: regio-, diastereo-, and enantiocontrolled photodimerization of anthracenecarboxylic acids.

Three kinds of enantiopure amphiphilic amino alcohols (1a-c) were newly synthesized, of which the stereochemistry of the stereogenic carbons adjacent to the amino (C2) and hydroxy (C1) groups was systematically varied. By using these amino alcohols and four photoreactive carboxylic acids, 12 kinds of salts were prepared. The structure and thermal behavior of the salts were thoroughly investigated by various techniques, which revealed that the stereochemistry of the amino alcohol unit has significant effects on the properties of the salts; the salts of 1a with (1R,2S)-configuration did not exhibit any liquid crystal (LC) phase but showed high crystallinity, whereas 1b and 1c with (1S,2S)- and (1S)-configurations, respectively, generally afforded stable LC salts with smectic structure(s). Within the matrix of these amphiphilic salts, the in situ photodimerizations of 2-anthracenecarboxylic acid (2c) and 1-anthracenecarboxylic acid (2d) were conducted by the irradiation with UV/vis light (500 W, a high-pressure mercury arc lamp, >380 nm). Concerning reactivity and regio-/diastereo-/enantioselectivities, the LC phases were found to be superior to isotropic and crystalline phases. For the two substrates 2c and 2d, every LC phase promoted the photodimerization with unprecedentedly high head-to-head selectivity. Particularly in the case of 2c, diastereoselecitivity (syn(HH) vs anti(HH)) could be rationally controlled by the choice of the amino alcohol unit and mesophase (syn(HH):anti(HH) = 61:37 to 26:72). Moreover, one of the LC phases exhibited by 1b·2c afforded the anti(HH)-dimer of 2c with excellent enantioselectivity (up to 86% ee). On the basis of the hypothesis that the present photochemical outcome arises from the preorientation of the substrates, a preliminary structural model of these LCs was proposed.

Operational problems of Haniwa net as a form of social capital: interdependence between human networks of physicians and information networks.

In August 2009, Miyazaki Health and Welfare Network (Haniwa Net, hereafter referred to as "the Net"), centrally led by University of Miyazaki Hospital (UMH), adopted a center hospital-based system offering a unilateral linkage that enables the viewing of UMH's medical records through a web-based browser (electronic medical records (EMR)). By the end of December 2010, the network had developed into a system of 79 collaborating physicians from within the prefecture. Beginning in August 2010, physicians in 12 medical institutions were visited and asked to speak freely on the operational issues concerning the Net. Recordings and written accounts were coded using the text analysis software MAXQDA 10 to understand the actual state of operations. Analysis of calculations of Kendall's rank correlation confirmed that the interdependency between human networks and information networks is significant. At the same time, while the negative opinions concerning the functions of the Net were somewhat conspicuous, the results showed a correlation between requests and proposals for operational improvements of the Net, clearly indicating the need for a more user-friendly system and a better viewer.

Influence of metal artifacts on in vivo micro-CT for orthodontic mini-implants.

This study aimed to show the effects of metal artifacts on the in vivo micro-CT of mini-implants by measuring bone volume. We drilled a hole in the cortical bone of a rat tibia and embedded a titanium orthodontic mini-implant (diameter, 1.5 mm) in the hole. Twelve individually weighed hydroxyapatite grains (HA grains) were placed around the implant either by one dentist (method 1) or separately by 12 dentists (method 2). In vivo micro-CT was used to scan the model after placement of each grain to measure increases and decreases in bone volume voxel number. The subtracted bone voxel volume increased with HA weight in both methods. Simple linear regression analysis showed a significant correlation between weight and volume in both methods (method 1: regression coefficient: 516.502, P < 0.05; method 2: regression coefficient: 4837.432, P < 0.05). Metal artifacts did not appear to influence measurements of bone volume, although further studies are required to determine the effect of thicker implants.

An image-guided technique for puncture of the superior temporomandibular joint cavity: clinical comparison with the conventional puncture technique.

OBJECTIVE: The objective of this study was to compare an image-guided puncture technique (IGPT) with conventional puncture technique (CPT) with respect to accuracy of needle entry, maximal mouth opening, and pain in pumping manipulation treatment of internal derangement of the temporomandibular joint (TMJ). STUDY DESIGN: The subjects comprised 178 patients with internal derangement of the TMJ with closed lock. Treatment was provided using CPT in 102 cases and IGPT in 76 cases. Three variables, number of repunctures, maximal mouth opening distance, and pain threshold according to a visual analogue scale, were measured and compared between IGPT and CPT groups. RESULTS: Access to the superior joint cavity was achieved without correcting the puncture point in 97% of patients who underwent IGPT and 82% of patients in the CPT group. Significant differences were seen in 1-week maximal mouth opening and pain threshold between IGPT and CPT groups (P < .05 each) and resetting of the puncture point was significantly less frequent using IGPT compared with CPT (P < .05). CONCLUSIONS: IGPT is effective for pain mitigation and improves mouth opening during the early postoperative period after pumping manipulation treatment.

Evaluation of the usefulness of magnetic resonance imaging in the assessment of the thickness of the roof of the glenoid fossa of the temporomandibular joint.

OBJECTIVE: The aim of this study was to evaluate the usefulness of magnetic resonance imaging (MRI) in measuring thickness of the roof of the glenoid fossa (RGF) of the temporomandibular joint (TMJ). STUDY DESIGN: Minimum RGF thickness in 95 TMJs of 59 patients with temporomandibular disorders were measured and compared on both sagittal-section MRI and cone-beam computed tomography (CBCT). RGF thickness on MRI was also compared with MRI, CBCT, and arthrographic findings. RESULTS: Minimum RGF thickness was greater on MRI (1.46 mm) than on CBCT (0.90 mm). Spearman's correlation coefficient by rank for these 2 types of measurements was 0.63. RGF thickness on MRI differed significantly between those with and without degenerative joint changes (1.69 vs 1.32 mm; P < .01) and between those with and without disk displacement (1.58 vs 1.35 mm; P = .04), but showed no associations with disk deformity, joint effusion, or disk perforation. CONCLUSIONS: MRI is useful in measuring RGF thickness from diagnostic as well as radiation protection standpoints.