Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions.

McMurry coupling is one of the most useful and convenient tools for the preparation of π-conjugated molecules. However, for the synthesis of strained macrocycles containing ethynylene linkages, reduction of ethynylene to vinylene linkage sometimes took place. Especially, for the synthesis of macrocyclic π-extended thiophene hexamers using McMurry coupling of dialdehyde 1 composed of three thienylene, two ethynylene, and two formyl groups, reduction of ethynylenes to vinylenes often takes place to produce unique products in a one-pot procedure, depending on very small steric and electronic effects such as reaction temperature, amounts of titanium reagent, and substituents of thiophene hexamers. The attractive structures and functional properties of reduced thiophene hexamers have been determined using X-ray analysis and OFET measurements.

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles.

Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3-cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO-LUMO gap and enhanced the near IR absorption property.

Effect of genu recurvatum on the anterior cruciate ligament-deficient knee during gait.

PURPOSE: This study aimed to investigate the effects of genu recurvatum, which is considered to carry a high risk for anterior cruciate ligament (ACL) injury, on healthy and post-ACL injury gait and lower extremity muscle strength. METHODS: Subjects were 36 patients with ACL-deficient knee and 40 healthy controls without pain or restricted range of motion of the lower extremity during gait. The knee joints of all subjects were examined; those with over 10° hyperextension of both knees were defined as exhibiting genu recurvatum. On this basis, the subjects were further subdivided into two groups: with or without genu recurvatum. A three-dimensional motion analysis system and force plates were used for gait analysis. Isokinetic dynamometers were used to measure knee muscle strength. RESULTS: There were no differences in joint angles, joint moments, or components of ground reaction force during gait or in knee strength for the healthy control subjects with and without genu recurvatum. ACL-deficient subjects without genu recurvatum showed a decrease in knee angles during the stance phase and a decrease in extension moments during the early stance phase compared with ACL-deficient subjects with genu recurvatum and controls. In contrast, neither knee angles nor extension moments during the stance phase differed significantly between ACL-deficient subjects with genu recurvatum and controls. CONCLUSIONS: This study provides clinically relevant information regarding the effects of genu recurvatum on gait parameters. The results suggest that in ACL injuries, the presence of genu recurvatum alters gait pattern. Consideration of the presence of genu recurvatum would be useful during rehabilitation following ACL injuries or ACL reconstruction. LEVEL OF EVIDENCE: II. Prospective comparative study.

Analysis of the kinematics of total knee prostheses with a medial pivot design.

Analysis of the kinematics of the FINE Total Knee System (Nakashima Medical, Okayama, Japan) revealed that the medial condyle is fixed and the lateral condyle shows lateral posterior movement and tibial internal rotation. Analysis of the kinematics of the ADVANCE Total Knee System (Wright Medical Technology, Arlington, Tenn) revealed that the medial condyle is fixed and the lateral condyle shows anterior movement in the early stage, changing thereafter to posterior movement. With regard to rotation, initial external rotation subsequently changes to internal rotation. Analysis of the kinematics of the ADVANTIM Total Knee System (Wright Medical Technology) revealed that the bicondyle shows posterior movement, subsequently changing to anterior and posterior movements. Thus, unlike the FINE or ADVANCE Total Knee Systems, the ADVANTIM Total Knee System shows internal rotation.

Quinoidal Oligothiophenes Having Full Benzene Annelation: Synthesis, Properties, Structures, and Acceptor Application in Organic Photovoltaics.

To achieve a complete closed-shell quinoidal state, bis(dicyanomethylene)-substituted quinoidal terthiophenes bearing benzene annelation at all thiophene rings were synthesized using a retro-Diels-Alder reaction as the key step. The unique structures and properties originating from the full benzene annelation were revealed by X-ray analysis as well as property measurements. Organic solar cells based on the combination of a donor polymer with a quinoidal terthiophene as an acceptor showed a power conversion efficiency of 1.39%.

Bilateral congenital separation of the lateral meniscus. A case report.

Reports of congenital abnormalities of the lateral meniscus include discoid meniscus, accessory meniscus, double-layered meniscus and ring-shaped meniscus. We present a rare case of an unusual abnormality of the bilateral lateral meniscus, which was completely separated and duplicated at the midportion, although different from an accessory meniscus, with an anomaly of the anterior horn of the medial meniscus as well as a double-layered medial meniscus. This type of abnormality of the lateral meniscus and double-layered medial meniscus has not previously been described in the literature. We have designated the abnormality of the bilateral lateral meniscus a separated meniscus.

Antiaromatic character of cycloheptatriene-bis-annelated indenofluorene framework mainly originated from heptafulvene segment.

Fully π-conjugated polycyclic hydrocarbons with antiaromatic character have attracted research attention because of their unique properties such as narrow energy gaps, and thus should find application as optical and electronic materials. Although antiaromatic 16π-electron frameworks can be constructed by the incorporation of multiple seven-membered rings in a fused fashion to install methylenecycloheptatriene (heptafulvene) segments, the development of corresponding benzo[1,2:4,5]di[7]annulene (BDA)-containing π-conjugated systems remains challenging due to the difficulty of their molecular design and synthesis. In this study, we develop an unprecedented chemical structure of cycloheptatriene-bis-annelated indenofluorene, which possesses both BDA and indenofluorene frameworks in a fused fashion. Physical measurements and X-ray analyses, along with theoretical calculations, indicated that antiaromaticity appeared in the BDA framework. By using the conjugated polycyclic hydrocarbon possessing both seven-membered and five-membered rings, this study provides fundamental insight into the strong antiaromatic nature of heptafulvene-based BDA framework.

Ni(II) tetrahydronorcorroles: antiaromatic porphyrinoids with saturated pyrrole units.

While hydrogenated porphyrins are abundant in natural and synthetic compounds, antiaromatic hydrogenated porphyrinoids have not been synthesized to date. Here, we report bacteriochlorin-like Ni(II) tetrahydronorcorrole complexes as the first examples of antiaromatic porphyrinoids that contain saturated pyrrole units.

Arthroscopic anatomical double-bundle anterior cruciate ligament reconstruction for asian patient using a bone-patellar tendon-bone and gracilis tendon composite autograft: a technical note.

BACKGROUND: Recent years have seen anterior cruciate ligament (ACL) reconstruction being performed in a broad range of patients, regardless of age, sex and occupation, thanks to great advances in surgical techniques, surgical instruments and basic research. In cases of ACL reconstruction, bone-patellar tendon-bone (BTB) graft or hamstring graft are frequency used. However, potential complications associated with tunnel enlargement due to soft tissue graft such as hamstring were reported. On the other hand, an altered rotational axis resulting in significantly greater translation of the lateral compartment in the single bundle compared with double bundle ACL reconstruction was reported. METHOD AND PROCEDURE: A reconstruction procedure was modified for the ACL using a double bundle that is the combination of BTB and gracilis tendon composite autograft. Two tibial and two femoral bone tunnels are used to reconstruct two bundles of ACL; an anteromedial bundle (AMB) and a posterolateral bundle (PLB). The femoral bone tunnels are created just posterior to the resident's ridge. The tibial bone tunnels are created at the center of AM and PL tibial attachment, respectively. BTB is fixed in the AM tunnels produced on the anatomical points of tibia and femur. The gracilis graft is fixed in an anatomical PL tunnel produced. The mean width of BTB is 7 mm, since10 mm graft is sometimes not suitable for patients, especially small Asian people and females. For these patients, 10 mm graft is bigger than one third of patella tendon width. CONCLUSION: The devised surgical procedure based on a combination of BTB and gracilis autograft is suitable reconstruction method for patients who have small or medium width of patellar tendon such as Asian people and females. This technique is also applicable to revision surgery.

Evaluation of human beta-enolase as a serum marker for exercise-induced muscle damage.

OBJECTIVE: To evaluate whether the serum beta-enolase level is a useful indicator of exercise-induced muscle damage in athletes. DESIGN: Blood samples were taken from 49 adult amateur marathon runners before and immediately after a marathon race, and the serum levels of beta-enolase and creatine phosphokinase were measured. SETTING: The Aoshima Taiheiyo Marathon 2000, Miyazaki, Japan, on a cloudy day in December with an ambient temperature of 18 degrees C. SUBJECTS: Forty-nine adult amateur marathon runners (42 men and 7 women) who regularly participated in runs. INTERVENTION: The intervention was a marathon run. MAIN OUTCOME MEASURES: Serum beta-enolase was measured using a sensitive sandwich enzyme-linked immunosorbent assay. Serum creatine phosphokinase was measured using a standard procedure. RESULTS: The mean beta-enolase concentration was 9.45 +/- 3.11 ng/mL before the race. It increased to 22.11 +/- 8.80 ng/mL after the race, representing a proportional increase of 1.57 +/- 1.46. The serum concentration of beta-enolase after the race was significantly higher than that before the race (P < 0.0001). Moreover, the serum beta-enolase level increased as much as the creatine phosphokinase level after the race, and strongly correlated with creatine phosphokinase (r = 0.828, P < 0.0001). The proportional increase of beta-enolase also correlated with that of creatine phosphokinase (r = 0.441, P < 0.005). CONCLUSIONS: Our data suggest that the absolute values of the serum beta-enolase are more appropriate to relate to muscle damage.