The superior capsule patch graft completely restored superior stability of the glenohumeral joint, while patch grafting to the supraspinatus tendon partially restored superior translation.
The thermal decomposition and isomerization processes of C3−C4 alkyl radicals, 1-C5H11, and 1-C6H13 have
been investigated by using a shock-tube apparatus coupled with atomic resonance absorption spectrometry
(ARAS). Isomeric alkyl radicals were generated by the thermal decomposition of respective alkyl iodides.
Branching fractions for the competitive pathways (C−C bond cleavage, C−H bond cleavage, and isomerization)
have been determined by following the hydrogen-atom concentration by ARAS. In the investigated temperature
range (900−1400 K), for all alkyl radicals, the energetically favored C−C bond cleavage was found to dominate
over the C−H bond cleavage. The 1,2 or 1,3 isomerization reaction was found to be minor in C3 and C4 alkyl
radicals. On the other hand, the results for 1-C5H11 and 1-C6H13 radicals clearly show the occurrence of 1,4
and 1,5 isomerization reactions. From an RRKM analysis of the present result and the previous lower
temperature data, with consideration of the tunneling effect, the threshold energies for 1,4 and 1,5 primary-to-secondary isomerization reactions were evaluated to be 21.5 ± 1.2 and 14.6 ± 1.2 kcal mol-1, respectively.
The high-pressure limit rate constants for the isomerization processes were evaluated as k
∞(1-C5H11 → 2-C5H11)
= 4.88 × 108
T
0.846 exp(−19.53 [kcal mol-1]/RT) s-1 and k
∞(1-C6H13 → 2-C6H13) = 6.65 × 107
T
0.823 exp(−12.45 [kcal mol-1]/RT) s-1 for the temperature range 350−1300 K. Even under relatively high-pressure
conditions (∼1 atm), the falloff effect was shown to be important for multichannel dissociation systems. The
nonequilibrium effect in the thermal decomposition of energized alkyl radicals formed in the high-temperature
reaction system, which has been first suggested by Tsang et al. [J. Phys. Chem.
1996, 100, 4011] was discussed.
The possible effect of the tunneling in the isomerization reactions was discussed in comparison with previous
lower temperature data.
Postoperative incomplete reduction of the sesamoids can be a risk factor for the recurrence of hallux valgus. The identification of incomplete reduction of the sesamoids intraoperatively may allow modification of surgical procedures and improvement of the surgical results.
Objective
The development and patterns of spontaneous aging-related changes in the anterior cruciate ligament (ACL) and their relationship to articular cartilage degeneration are not well characterized. The aim of this study was to investigate the types and temporal sequence of aging-related ACL changes and establish the correlation with cartilage lesion patterns at all stages of OA development in human knee joints without prior joint trauma.
Methods
Human knee joints (n=120; 65 donors; age 23-92) were obtained at autopsy and ACL and cartilage were graded macroscopically and histologically. Inflammation surrounding the ACL was assessed separately.
Results
Histological ACL substance scores and ligament sheath inflammation scores increased with aging. Collagen fiber disorganization was the earliest and most prevalent change. The severity of mucoid degeneration and chondroid metaplasia in the ACL increased with development of cartilage lesions. A correlation between ACL and cartilage degeneration was observed, especially in the medial compartment of the knee joint.
Conclusion
ACL degeneration is highly prevalent in knees with cartilage defects, and may even precede cartilage changes. Hence, ACL deficiencies may not only be important in post-traumatic OA, but also a feature associated with knee OA pathogenesis in general.
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