A new class of eight-membered Sn2P2O4 heterocycles. Crystal structure and electrolytic dissociation in solution of cyclo-[R2Sn(OPPh2O)2SnR2](O3SCF3)2(R=Me, t-Bu)

The syntheses of cyclo-[R₂Sn(OPPh₂O)₂SnR₂](O₃SCF₃)₂ (R = Me (1), t-Bu (2)) by the consecutive reaction of R₂SnO (R = Me, t-Bu) with triflic acid and diphenylphosphinic acid are presented. In the solid state, 1 and 2 were investigated by ¹¹⁹Sn MAS and ³¹P MAS NMR spectroscopy as well as X-ray crystallography and appear to exist as ion pairs of cyclo-[R₂Sn(OPPh₂O)₂SnR₂]²⁺ dications and triflate anions. In solution, 1 and 2 are involved in extensive equilibria processes featuring cationic diorganotin(IV) species with Sn-O-P linkages, as evidenced by ¹¹⁹Sn and ³¹P NMR spectroscopy, electrospray mass spectrometry, and conductivity measurements.

Oligomethylene-bridged dinuclear triorganotin triflates and diphenylphosphinates. Ion pairing in the solid state and electrolytic dissociation in solution of [Ph2Sn(CH2)nSnPh2X](O3SCF3) (X = OH, O2PPh2; n = 1-3)

The condensation of [Ph₂(OH)Sn(CH₂)_nSn(OH)Ph₂] (1-3; n = 1-3) with HO₃SCF₃ and HO₂PPh₂ provided [Ph₂Sn(CH₂)_nSnPh₂(OH)](O₃SCF₃) (4-6; n = 1-3) and [Ph₂(O₂PPh₂)Sn(CH₂)_nSn(O₂PPh₂)Ph₂] (10-12; n = 1-3), respectively. The reaction of [Ph₂Sn(CH₂)_nSnPh₂(OH)](O₃SCF₃) (4-6; n = 1-3) with HO₂PPh₂ and NaO₂PPh₂ gave rise to the formation of [Ph₂Sn(CH₂)_nSnPh₂(O₂PPh₂)](O₃SCF₃) (7-9; n = 1-3) and [Ph₂(OH)Sn(CH₂)_nSn(O₂PPh₂)Ph₂] (13-15; _n = 1-3), respectively. In the solid state, compounds 4-9 comprise ion pairs of cationic cyclo-[Ph₂SnCH₂SnPh₂(OH)]₂²⁺, cyclo-[Ph₂Sn(CH₂)_nSnPh₂(OH)]⁺ (n = 2, 3), and cyclo-[Ph₂Sn(CH₂)_nSnPh₂(O₂PPh₂)]⁺ (n = 1-3) and triflate anions. In MeCN, the eight-membered-ring system cyclo-[Ph₂SnCH₂SnPh₂(OH)]₂²⁺ appears to be in equilibrium with the four-membered-ring system cyclo-[Ph₂SnCH₂SnPh₂(OH)]⁺. In contrast, compounds 10-15 show no ionic character. Compounds 1-15 were characterized by multinuclear NMR spectroscopy in solution and in the solid state, IR spectroscopy, conductivity measurements, electrospray mass spectrometry, osmometric molecular weight determinations, and X-ray crystallography (4, 5, 7, and 12).

Alterations in the proportions of skeletal muscle proteins following a unilateral lesion to the substantia nigra pars compacta of rats

It is well established that mammalian skeletal muscles exhibit a considerable degree of plasticity and one of the main determining factors of this plasticity is the activity pattern and duration of motoneurone discharge. Lesions to the right substantia nigra pars compacta (SNpc) of six adult rats were made to determine whether altered output from the SNpc ultimately leads to a change in the expression of proteins in contralateral skeletal muscles. After 4 months, altered motor performance was identified by the administration of amphetamine. After 7 months, 30–70% of dopaminergic cells in the SNpc had been destroyed. The protein content of muscles was then quantified from densitometric scans of gels, and expressed as a % of the amount of actin (the protein used as a reference in this study). The lesion affected the expression of different protein isoforms in the fast- and slow-twitch muscles. In slow-twitch soleus muscles, the lesion decreased the proportion of α-tropomyosin and increased the proportion of β-tropomyosin. In the fast-twitch extensor digitorum longus muscles, the lesion increased the proportion of the fast isoform of troponin-T_1f, and decreased the proportions of the two isoforms of myosin light chain. This study establishes a connection between the chronic effects of a lesion to the SNpc, with a loss of dopaminergic neurones, impaired motor performance, and altered expression of proteins in skeletal muscle. The implication of these results is that the altered motor function observed in Parkinson’s disease may be associated with alterations to the expression of skeletal muscle proteins.

Temporal expression of heat shock proteins 60 and 70 at lesion-prone sites during atherogenesis in ApoE-deficient mice

In the study, we investigate whether the expressions of heat shock protein (hsp)60 (a potential autoantigen) and the stress-inducible form of cytoprotector hsp70 are correlated with the development of atherosclerotic lesions in the aortic tree of apolipoprotein E–deficient (apoE^-/-) mice. The apoE^-/- mouse model is advantageous because the stress-inducible form of hsp70 is not constitutively expressed in mice, unlike primates; hence, tissues under stress can be clearly defined. Both mammalian hsps were detected newly expressed (before mononuclear cell infiltration) on aortic valves and endothelia at lesion-prone sites of 3-week-old apoE^-/- mice. In 8- and 20-week-old mice, they were strongly and heterogeneously expressed in early to advanced fibrofatty plaques, with levels correlating with lesion severity. Expression was markedly downregulated in advanced collagenous, acellular, calcified plaques of 40- and 69-week-old mice and was absent in control aortas of normocholesterolemic wild-type (apoE^+/+) mice. Western blot analysis of tissue homogenates confirmed the temporal expression of the hsps. Double immunostaining revealed that both hsps were expressed by lesional endothelial cells, macrophages, smooth muscle cells, and CD3⁺ T lymphocytes. This study provides evidence that hsp60 and hsp70 are temporally expressed on all major cell types in lesion-prone sites during atherogenesis, suggesting that few cells escape the toxic environment of the atherosclerotic plaque.

Arthroscopic repair of humeral avulsion of glenohumeral ligament lesion : anterior and posterior techniques

Humeral avulsion of the inferior glenohumeral ligament complex is an unusual pathology, often implicated in traumatic shoulder instability. Traditional open techniques involve at least partial detachment of the subscapularis, and arthroscopic techniques are limited by neurovascular boundaries. The technique described here presents an anterior and posterior arthroscopic approach that can be used individually or in combination to treat different types of humeral avulsion of the inferior glenohumeral ligament lesions. The anterior approach is based on anatomic guidelines described in the literature. The posterior approach is based on the arthroscopic and cadaveric anatomic studies described by one of the authors (D.N.B.); use of the recently described axillary pouch portal (Bhatia portal) permits safe arthroscopic instrumentation access in the entire inferior glenohumeral recess and provides adequate access to the posteroinferior aspect of the humeral head. The differential mattress stitch technique ensures secure fixation of the avulsed ligaments and eliminates excessive capsular redundancy. Technical tips to avoid complications are discussed, and a detailed rehabilitation protocol is presented.

Arthroscopic repair of a chondrolabral lesion associated with anterior glenohumeral dislocation

Chondrolabral lesions are uncommon after anteroinferior glenohumeral dislocations. This report describes a new dual-lesion complex that involved an avulsion of the anteroinferior glenoid labrum and a flap tear of the adjacent articular cartilage [glenoid labral tear and articular cartilage flap (GLAF) lesion]. The chondral component involved a large undermined region of the anterior half of the lower glenoid articular cartilage, and the labral component involved an avulsion from the 2.30–6 o’clock position on the glenoid. The labral tear was reconstructed with 3 suture anchors to form a neo-labrum in an attempt to overlap and stabilize the periphery of the chondral flap. A meniscal repair device was used to place a mattress stitch in the cartilage periphery to further stabilize the flap. This technique resulted in a secure repair without any chondral damage, and this remained intact on an MRI performed at a 3-month follow-up. A final 12-month follow-up showed complete recovery, as assessed by the Oxford shoulder instability score and Rowe score, and by a return to the pre-injury sporting level.

Cathode characterization with steel and copper collector bars in an electrolytic cell

This article presents finite-element method simulation results of current distribution in an aluminum electrolytic cell. The model uses one quarter of the cell as a computational domain assuming longitudinal (along the length of the cell) and transverse axes of symmetries. The purpose of this work is to closely examine the impact of steel and copper collector bars on the cell current distribution. The findings indicated that an inclined steel collector bar (φ = 1°) can save up to 10–12 mV from the cathode lining in comparison to a horizontal 100 mm × 150-mm steel collector bar. It is predicted that a copper collector bar has a much higher potential of saving cathode voltage drop (CVD) and has a greater impact on the overall current distribution in the cell. A copper collector bar with 72% of cathode length and size of 100 mm × 150 mm is predicted to have more than 150 mV savings in cathode lining. In addition, a significant improvement in current distribution over the entire cathode surface is achieved when compared with a similar size of steel collector bar. There is a reduction of more than 70% in peak current density value due to the higher conductivity of copper. Comparisons between steel and copper collector bars with different sizes are discussed in terms CVD and current density distribution. The most important aspect of the findings is to recognize the influence of copper collector bars on the current distribution in molten metal. Lorentz fields are evaluated at different sizes of steel and copper collector bars. The simulation predicts that there is 50% decrease in Lorentz force due to the improvement in current distribution in the molten metal.

Ecotypic variation in the response of Arabidopsis thaliana to Phytophthora cinnamomi

A variety of reactions to inoculation with Phytophthora cinnamomi ranging from high susceptibility to moderate resistance were found in 20 ecotypes of Arabidopsis thaliana. P. cinnamomi zoospores successfully colonised both root and leaf tissue of Arabidopsis and sporulation in the form of chlamydospores and sporangia occurred in leaves and roots of each ecotype but the number varied considerably between ecotypes. In the more susceptible ecotypes, colonisation was characterised by rapid intercellular growth and sporulation of the pathogen from 48 h post inoculation. In less susceptible ecotypes, P. cinnamomi was limited to a defined region within tissues. In response to P. cinnamomi infection, several ecotypes expressed active defence responses in both root and leaf tissue. Callose formation was closely associated with lesion restriction as was the production of the reactive oxygen species, hydrogen peroxide. The oxidative burst was not limited to the site of pathogen ingress but also occurred in distant, uninfected tissues. We have characterised an Arabidopsis–P. cinnamomi system that will be useful for further studies of active resistance mechanisms.

"I could see, and yet, mon, I could na` see" : William Macewen, the agnosias, and brain surgery

Two little noticed cases in which William Macewen used symptoms of visual agnosia to plan brain surgery on the angular gyrus are reviewed and evaluated. Following a head injury, Macewen’s first patient had an immediate and severe visual object agnosia that lasted for about 2 weeks. After that he gradually became homicidal and depressed and it was for those symptoms that Macewen first saw him, some 11 months after the accident. From his examination, Macewen concluded that the agnosia clearly indicated a lesion in “the posterior portion of the operculum or in the angular gyrus.” When he removed parts of the internal table that had penetrated those structures the homicidal impulses disappeared. Macewen’s second patient was seen for a chronic middle ear infection and, although neither aphasic nor deaf, was ‘word deaf.’ Slightly later he became ‘psychically blind’ as well. Macewen suspected a cerebral abscess pressing on both the angular gyrus and the first temporal convolution. A large subdural abscess was found there and the symptoms disappeared after it was treated. The patients are discussed and Macewen’s positive results analysed in the historical context of the dispute over the proposed role of the angular gyrus as the visual centre.

Asymptomatic hypoechoic regions on patellar tendon ultrasound : a 4-year clinical and ultrasound followup of 46 tendons

Patellar tendon ultrasound appearance is commonly used in clinical practice to diagnose patellar tendinopathy and guide management. Using a longitudinal study design we examined whether or not the presence of a hypoechoic ultrasonographic lesion in an asymptomatic patellar tendon conferred a risk for developing jumper's knee compared with a tendon that was ultrasonographically normal. Ultrasonographic, symptomatic and anthropometric assessment was completed at baseline and followup. Magnetic resonance imaging was performed on four tendons that resolved ultrasonographically in the study period. Forty-six patellar tendons were followed over 47±11.8 months. Eighteen tendons were hypoechoic at baseline and 28 were ultrasonographically normal. Five tendons resolved ultrasonographically in the study period. Magnetic resonance imaging in four of these tendons was normal. Seven normal patellar tendons at baseline developed a hypoechoic area but only two became symptomatic. Analysis of ultrasonography at baseline and clinical outcome with Fisher's exact test shows there is no association between baseline ultrasound changes and symptoms at followup. In this study there is no statistically significant relationship between ultrasonographic patellar tendon abnormalities and clinical outcome in elite male athletes. Management of jumper's knee should not be solely based on ultrasonographic appearance; clinical assessment remains the cornerstone of appropriate management.

The reactivity of bis(para-methoxyphenyl)telluroxide towards triflic acid and diphenylphosphinic acid. Theoretical considerations of the protonation and hydration process of diorganotelluroxanes

The reaction of (p-MeOC₆H₄)₂TeO with two equivalents of HO₃SCF₃ and HO₂PPh₂ provided the tetraorganoditelluroxanes (F₃CSO₃)(p-MeOC₆H₄)₂TeOTe(p-MeOC₆H₄)₂(O₃SCF₃) (1) and (Ph₂PO₂)(p-MeOC₆H₄)₂TeOTe(p-MeOC₆H₄)₂(O₂PPh₂)·2 Ph₂PO₂H (2) in good yields. Compounds 1 and 2 were characterized by solution and solid-state ³¹P and ¹²⁵Te NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements and single crystal X-ray diffraction. In solution, compound 1 undergoes an electrolytic dissociation and reversibly reacts with traces of water to give the mononuclear cation [(p-MeOC₆H₄)₂TeOH]⁺ and triflate anions. Theoretical aspects of the protonation and hydration of model telluroxanes R₂TeO (R = H, Me, Ph) were investigated by preliminary DFT calculations and compared to the corresponding selenoxanes R₂SeO. The tellurium dihydroxides R₂Te(OH)₂ seem to be more stable than the hydrogen-bonded complexes R₂TeO·H₂O.