Surgical management of facet cysts in the thoracic spine: Radiological manifestations and results of fenestration.

BACKGROUND: Facet cysts in the thoracic spine are a rare cause of thoracic myelopathy. We aimed to investigate the clinical/radiological features and surgical results of these lesions. METHODS: Nine thoracic facet cysts in eight patients (seven men, one woman) were diagnosed based on magnetic resonance imaging (MRI) and computed tomography (CT) with facet arthrography findings and surgically treated. The mean patient age was 71 (59-83) years. The cysts were distributed as follows: one each at T8-9 and T9-10, two each at T1-2 and T11-12, and three at T10-11. The mean follow-up period was 1.8 (1-5) years. Clinical and radiological features were retrospectively investigated, and surgical outcomes were evaluated according to modified Japanese Orthopaedic Association (JOA) scores for thoracic myelopathy (full score: 11). RESULTS: Neurological examination revealed progressive thoracic transverse myelopathy in all patients with a mean disease duration of 1.2 months (2 weeks-2 months). MRI revealed a total of nine cysts across the eight patients: four in the median region and five in the paramedian portion of the spinal canal. CT revealed degeneration in all involved facet joints. All the cysts were in communication with the neighboring facet joint confirmed by CT facet arthrography. All patients underwent bilateral fenestration, and the cysts were resected with the ligamentum flavum. The mean preoperative and postoperative modified JOA scores were 4.5 and 8.8, respectively. The mean recovery rate was 67.5%. Differences in the degree of local kyphosis were 2° or less between before and after surgery. On histopathology, synovial lining cells were not noted in any case. CONCLUSIONS: Decompression surgery is recommended for treating progressive myelopathy in patients with cystic lesions. Our study suggests that thoracic facet cyst resection with satisfactory surgical outcomes would be possible through fenestration.

Titanium Germylidenes.

Two novel 18-electron titanium germylene complexes, Cp2 Ti(L)=Ge[Si3 (SiMet Bu2 )4 ] 3 b (L=Me3 P) and 3 c (L=XylNC), were synthesized, isolated, and structurally characterized. The length of the titanium-germanium bonds of 2.5387(3) Šand 2.5276(3) Š(in 3 b and 3 c, respectively) well match those expected for the double bond, which was further supported by the DFT study. Based on their structural characteristics, as well as their atomic charges calculations which revealed Ti(δ+)=Ge(δ-) bond polarization, both 3 b and 3 c are classified as the Schrock-type titanium germylidenes, as the germanium analogues of the widely known titanium alkylidenes. By contrast, germylene complexes of the group 6 metals 8 a (M=Mo) and 8 b (M=W) are better described as Fischer-type germylene complexes.

Co(I) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal-ligand cooperation platform.

A series of low spin cobalt(i) complexes bearing a tetradentate phenanthroline-based PNNP ligand (2,9-bis((diphenylphosphanyl)methyl)-1,10-phenanthroline), [CoCl(PNNP)] (1), [CoMe(PNNP)] (2) and [Co(CH2SiMe3)(PNNP)] (3), were synthesized and structurally identified. Complex 3 underwent a structural rearrangement of the PNNP skeleton upon heating to form [Co(PNNP')] (4), which is supported by an asymmetrical PNNP' ligand with a dearomatized phenanthroline backbone. Mechanistic studies supported that the transformation from 3 to 4 was initiated by the homolysis of either a Co-CH2SiMe3 bond or a benzylic C-H bond. Complex 4 achieved H-H bond cleavage of H2 (1 atm) at ambient temperature, to form [Co(PNNP'')] (6), in which two H atoms were incorporated into the endocyclic double bond of the PNNP'' ligand backbone.

From a (Silatrigerma)cyclobutenylium Ion to a (Silatrigerma)cyclobutenyl Radical and Back.

(Silatrigerma)cyclobutenylium ion salt 2+·[B(C6F5)4]- was readily prepared by the reaction of cyclotrigermene 1 with an equimolar amount of [Et3Si(benzene)]+·[B(C6F5)4]- in benzene. The homoaromatic nature of 2+ was firmly established by its crystallographic analysis, which revealed a highly folded SiGe3 four-membered ring (40.4°) and a remarkably short transannular Ge-Ge distance of 2.9346(3) Å. The homoaromaticity of 2+ was supported by DFT calculations, which confirmed an extensive transannular bonding orbital interaction. One-electron reduction of 2+·[B(C6F5)4]- with potassium graphite resulted in the selective formation of (silatrigerma)cyclobutenyl free radical 2·, which has an allylic-type structure as confirmed by its X-ray and EPR studies. Cation 2+ and free radical 2· can be readily interconverted, thus constituting a fully reversible redox pair.

Anterior Decompression and Fusion Versus Laminoplasty for Cervical Myelopathy Caused by Soft Disk Herniation: A Long-term Prospective Multicenter Study.

STUDY DESIGN: A prospective multicenter study. OBJECTIVE: The purpose of this study was to determine whether laminoplasty (LP) is comparable for myelopathy caused by cervical disk herniation (CDH). SUMMARY OF BACKGROUND DATA: Anterior decompression and fusion (ADF) has conventionally been used for myelopathy caused by CDH with stable outcomes. However, recurrence of myelopathy due to adjacent segment degeneration are its drawbacks. The efficacy of LP without discectomy has been sporadically reported, but no long-term prospective study has been conducted to verify it. MATERIALS AND METHODS: Patients with cervical myelopathy caused by CDH were studied. The first 30 patients and the next 30 patients were treated with ADF and LP, respectively. The outcomes were compared between the 22 ADF patients and the 20 LP patients who had completed the follow-up examination scheduled 10 years after surgery. RESULTS: There was no statistically significant difference in the postoperative severity or recovery rate of myelopathy between the 2 groups 10 years after surgery. One patient in the ADF group underwent LP for secondary myelopathy due to adjacent segment degeneration 2 years after the surgery. Reoperation was not required for patients in the LP group. Postoperative neck pain was significantly more severe in the LP group than in the ADF group. CONCLUSIONS: ADF and LP for cervical myelopathy caused by CDH achieve similarly favorable outcomes. Recurrence of myelopathy caused by adjacent segment degeneration is a disadvantage of ADF while residual neck pain is a disadvantage of LP.

Tuning Philicity of Dichlorosilylene: Nucleophilic Behavior of the Dichlorosilylene-NHC Complex Cl2Si-IPr.

Novel unsaturated four-membered ring disilene, 3,3-dichloro-1,2,4,4-tetrakis[di-tert-butyl(methyl)silyl]-1Δ-1,2,3,4-trisilagermetene, was synthesized by the ring expansion reaction of the three-membered ring 1-disilagermirene with the silylene-NHC complex Cl2Si-IPr. The mechanism of the unexpected formation of this compound was verified by high-level density functional theory computations, which revealed nSi:(HOMO)-πSi=Si(LUMO) * as the dominant orbital interaction.

Rare-Earth Cyclobutadienyl Sandwich Complexes: Synthesis, Structure and Dynamic Magnetic Properties.

The potassium cyclobutadienyl [K2 {η4 -C4 (SiMe3 )4 }] (1) reacts with MCl3 (THF)3.5 (M=Y, Dy) to give the first rare-earth cyclobutadienyl complexes, that is, the complex anions [M{η4 -C4 (SiMe3 )4 }{η4 -C4 (SiMe3 )3 -κ-(CH2 SiMe2 }]2- , (2M ), as their dipotassium salts. The tuck-in alkyl ligand in 2M is thought to form through deprotonation of the "squarocene" complexes [M{η4 -C4 (SiMe3 )4 }2 ]- by 1. Complex 2Dy is a single-molecule magnet, but with prominent quantum tunneling. An anisotropy barrier of 323(22) cm-1 was determined for 2Dy in an applied field of 1 kOe, and magnetic hysteresis loops were observed up to 7 K.

Arsagermene, a compound with an -As[double bond, length as m-dash]Ge[double bond splayed right] double bond.

The first compound featuring an As[double bond, length as m-dash]Ge double bond, arsagermene Mes*As[double bond, length as m-dash]Ge(SiMetBu2)2, was synthesized, isolated and fully characterized. Crystallographic studies revealed that arsagermene has a planar Ge[double bond, length as m-dash]As bond of 2.2731(8) Å, which is notably shorter than the standard Ge-As single bond. The double bond character of arsagermene was further supported by computational data.

From Borapyramidane to Borole Dianion.

Nonclassical pyramidanes with their inverted tetrahedral configuration of the apical atom are among the most challenging synthetic targets in cluster chemistry. In this Communication, we report on the synthesis and structure of the first representative of pyramidal compounds with the group 13 element at the apex, namely, chloroborapyramidane 2. Reduction of 2 with excess of lithium metal unexpectedly produced the cage-opening product, borole dianion derivative {32-·[Li(thf)+]2}, a 6π-electron aromatic system.

Clinical features and radiological findings of 67 patients with SAPHO syndrome.

OBJECTIVES: The purpose of this study was to facilitate the understanding of the SAPHO (Synovitis, Acne, Pustulosis, Hyperostosis, and Osteitis) syndrome by analyzing the clinical and radiological features of 67 Japanese patients with SAPHO syndrome. METHODS: Sixty-seven Japanese patients (female/male: 44/23, mean age at onset: 48.5 years) were diagnosed with SAPHO syndrome from 2002 to 2013 at our hospital. Medical records and radiological imaging of these patients were retrospectively reviewed. RESULTS: Among the 67 patients, 41 had dermatological manifestations, such as palmoplantar pustulosis, acne, and psoriasis. Initial symptom was local pain in all patients, and the most common initial site of the symptom was the anterior chest. Bacterial and fungal cultures from 20 bone biopsies were all negative. Histopathological diagnosis of the specimens was non-specific inflammation in all cases. Bone lesions were observed in 65 patients (97.0%). On the other hand, articular lesions including enthesitis were found in 31 patients (46.2%). CONCLUSION: SAPHO syndrome had different clinical and radiological aspects. The clinical features were not remarkable, except the dermatological manifestations and the involvement of the anterior chest. Bone lesions including hyperostosis and osteitis were found radiographically in the majority of patients with SAPHO syndrome. These are the characteristics of the SAPHO syndrome, with the exclusion of other bone diseases.

Bis(stibahousene).

Strained hydrocarbons constitute one of the most prominent classes of organic compounds. Among them, bicyclo[2.1.0]pentene ("housene") derivatives represent a highly challenging and very attractive class. Although organic housenes have been known for more than five decades, there are still very few of them containing heavier main group elements. In this paper, we report on the two housene-type structures, novel monomeric stibahousene and dimeric bis(stibahousene). The bonding natures of both compounds were approached from both experimental and computational directions to reveal their peculiar structural features.

Spectroscopic Observation of the Triplet Diradical State of a Cyclobutadiene.

Tetrakis(trimethylsilyl)cyclobuta-1,3-diene (1) was subjected to a temperature-dependent EPR study to allow the first spectroscopic observation of a triplet diradical state of a cyclobutadiene (2). From the temperature dependent EPR absorption area we derive a singlet→triplet (1→2) energy gap, EST , of 13.9 kcal mol-1 , in agreement with calculated values. The zero-field splitting parameters D=0.171 cm-1 , E=0 cm-1 are accurately reproduced by DFT calculations. The triplet diradical 2 is thermally accessible at moderate temperatures. It is not an intermediate in the thermal cycloreversion of cyclobutadiene to two acetylene molecules.

Rapamycin suppresses microglial activation and reduces the development of neuropathic pain after spinal cord injury.

Rapamycin is an inhibitor of the mammalian target of rapamycin (mTOR) signaling pathway, plays an important role in multiple cellular functions. Our previous study showed rapamycin treatment in acute phase reduced the neural tissue damage and locomotor impairment after spinal cord injury (SCI). However, there has been no study to investigate the therapeutic effect of rapamycin on neuropathic pain after SCI. In this study, we examined whether rapamycin reduces neuropathic pain following SCI in mice. We used a mouse model of thoracic spinal cord contusion injury, and divided the mice into the rapamycin-treated and the vehicle-treated groups. The rapamycin-treated mice were intraperitoneally injected with rapamycin (1 mg/kg) 4 h after SCI. The rapamycin treatment suppressed phosphorylated-p70S6K in the injured spinal cord that indicated inhibition of mTOR. The rapamycin treatment significantly improved not only locomotor function, but also mechanical and thermal hypersensitivity in the hindpaws after SCI. In an immunohistochemical analysis, Iba-1-stained microglia in the lumbar spinal cord was significantly decreased in the rapamycin-treated mice. In addition, the activity of p38 MAPK in the lumbar spinal cord was significantly attenuated by rapamycin treatment. Furthermore, phosphorylated-p38 MAPK-positive microglia was relatively decreased in the rapamycin-treated mice. These results indicated rapamycin administration in acute phase to reduce secondary neural tissue damage can contribute to the suppression of the microglial activation in the lumbar spinal cord and attenuate the development of neuropathic pain after SCI. The present study first demonstrated that rapamycin has significant therapeutic potential to reduce the development of neuropathic pain following SCI. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:93-103, 2017.

A Cationic Phosphapyramidane.

Pyramidanes C[C4 R4 ] constitute a novel class of highly strained and reactive polyhedral clusters that attracted a great deal of attention of both theoreticians and experimentalists. Although well-studied from the theoretical viewpoint, pyramidanes were synthetically inaccessible, and only very recently their very first isolable representatives have been described. In this Communication, we report on the synthesis and structural studies of the cationic pyramidane with the Group 15 element at the apex, namely, phosphapyramidane, an isoelectronic analogue of the neutral pyramidanes of the Group 14 elements.

Isolation of Hypervalent Group-16 Radicals and Their Application in Organic-Radical Batteries.

Using a newly prepared tridentate ligand, we isolated hypervalent sulfur and selenium radicals for the first time and characterized their structures. X-ray crystallography, electron spin resonance spectroscopy, and density functional theory calculations revealed a three-coordinate hypervalent structure. Utilizing the reversible redox reactions between hypervalent radicals and the corresponding anions bearing Li(+), we developed organic radical batteries with these compounds as cathode-active materials. Furthermore, an all-radical battery, with these compounds as the cathode and a silyl radical as the anode, was developed that exhibited a practical discharge potential of ∼ 1.8 V and stable cycle performance, demonstrating the potential of these materials for use in metal-free batteries that can replace conventional Li-ion batteries where Li is used in the metal form.

From a Si3-Cyclopropene to a Si3S-Bicyclo[1.1.0]butane to a Si3S-Cyclopropene to a Si3S2-Bicyclo[1.1.0]butane: Back-and-Forth, and In-Between.

Compact and highly reactive bicyclo[1.1.0]butanes constitute one of the most fascinating classes of organic compounds. Furthermore, interplay of bicyclo[1.1.0]butanes with their valence isomers, such as buta-1,3-dienes and cyclobutenes, is among the fundamental pericyclic transformations in organic chemistry. Herein we report the back-and-forth interconversion between the cyclotrisilenes and thiatrisilabicyclo[1.1.0]butanes, allowing for the synthesis of novel representatives of such classes of highly reactive organometallics. The peculiar structural and bonding features of the newly synthesized compounds, as well as the mechanism of their isomerization, were verified both experimentally and computationally.

Observation of a thermally accessible triplet state resulting from rotation around a main-group π†bond.

We report the first direct spectroscopic observation by electron paramagnetic resonance (EPR) spectroscopy of a triplet diradical that is formed in a thermally induced rotation around a main-group π bond, that is, the SiSi double bond of tetrakis(di-tert-butylmethylsilyl)disilene (1). The highly twisted ground-state geometry of singlet 1 allows access to the perpendicular triplet diradical 2 at moderate temperatures of 350-410 K. DFT-calculated zero-field splitting (ZFS) parameters of 2 accurately reproduce the experimentally observed half-field transition. Experiment and theory suggest a thermal equilibrium between 1 and 2 with a very low singlet-triplet energy gap of only 7.3 kcal mol(-1) .

Improving battery safety by reducing the formation of Li dendrites with the use of amorphous silicon polymer anodes.

To provide safe lithium-ion batteries (LIBs) at low cost, battery materials which lead to reduced Li dendrite formation are needed. The currently used anode materials have low redox voltages that are very close to the redox potential for the formation of Li metal, which leads to severe short circuiting. Herein, we report that when the three-dimensional amorphous silicon polymers poly(methylsilyne) and poly(phenylsilyne) are used as anode materials, dendritic Li formation on the anode surface is avoided up to a practical current density of 10 mA·g(-1) at 5 °C. Equally as significant, poly(methylsilyne) and poly(phenylsilyne) are capable of reacting with 0.45 and 0.9 Li atoms per formula unit, respectively, at an average voltage of approximately 1.0 V, affording reversible capacities of 244 mAh·g(-1) and 180 mAh·g(-1). Moreover, noteworthy is the fact that polysilynes are suitable for practical applications because they can be prepared through a simple and low-cost process and are easy to handle.

Pentagermapyramidane: crystallizing the "transition-state" structure.

The first example of the homonuclear pyramidanes, pentagermapyramidane, was synthesized, fully characterized, and computationally studied to reveal its peculiar structural features and the nature of its apex-to-base bonding interactions. Both solid-state and solution structures of pentagermapyramidane are discussed based on the computed stabilities of its square-pyramidal and distorted forms.