Simultaneous determination of five carbapenems, highly polar antibiotics, in milk by LC-MS/MS.

The simultaneous determination of five carbapenems (biapenem, doripenem, ertapenem, imipenem, and meropenem) in raw and pasteurised bovine milk samples using LC-MS/MS was achieved and validated. Chromatographic separation was conducted on an InertSustain® AQ-C18 column using 0.1% formic acid in water and acetonitrile as the mobile phase. Target compounds were extracted using acetonitrile/water (20:80, v/v). After the removal of lipids with acetonitrile-saturated hexane, the dissolved protein was denatured with acetic acid. A portion of the supernatant was passed through an Oasis® PRiME HLB cartridge to remove the matrix. This novel method was validated in accordance with the Japanese validation guidelines and exhibited good trueness, ranging from 86.3% to 96.2%, using matrix-matched calibration curves. The relative standard deviation of repeatability ranged from 1.0% to 6.3%, and that of within-laboratory reproducibility ranged from 1.6% to 7.1%. The limit of quantification was 1.0 µg kg-1 for all analytes. None of the 60 milk samples commercially available in Tokyo contained any analytes. This novel method exhibited high-quality performance and can easily be implemented for the routine monitoring of carbapenems, which are highly polar antibiotics in milk.

Does vacuum phenomenon at non-fused discs affect the postoperative course after transforaminal lumbar interbody fusion in patients showing a positive value of difference in lumbar lordosis?

INTRODUCTION: Preoperative difference in lumbar lordosis (DiLL) was associated with surgical outcomes after single-level transforaminal lumbar interbody fusion (TLIF). Patients with DiLL>0 (DiLL (+)) tended to show worse clinical outcomes and postoperative greater restoration of lumbar lordosis (LL). However, some patients with DiLL (+) showed relatively good outcomes and no postoperative LL restration. This study aimed to elucidate whether the lumbar intervertebral disc vacuum phenomenon (VP) influences clinical course after single-level TLIF in patients with DiLL (+) and DiLL (-). METHODS: Patients with lumbar spinal stenosis and degenerative spondylolisthesis treated with single-level TLIF were included. Pre- and postoperative LL were measured, and postoperative LL improvement was calculated. Preoperative DiLL was calculated as preoperative supine LL minus standing LL. Severity of VP at the non-fused discs (SVP (non-FS)) was evaluated using preoperative reconstructed computed tomography imaging. Clinical outcomes were assessed using the Oswestry disability index, visual analogue scale (VAS; low back pain (LBP), lower-extremity pain, numbness, and the Japanese Orthopaedic Association Back Pain Evaluation Questionnaire. Patients were stratified by the median preoperative SVP (non-FS) score into severe and mild VP groups in patients with DiLL (+) or DiLL (-), and their surgical outcomes were compared. RESULTS: Overall, 89 patients were included. In patients with DiLL (+) (n = 37), patients with severe VP showed worse clinical outcomes, particulary for LBP and DiLL (+) patients with mild VP showed greater LL improvement (6.5° ± 10.0°). In patients with DiLL(-) (n = 52), patients with severe VP showed worse clinical outcomes, particularly for LBP and no differences in preoperative, postoperative, and improvement of LL were observed between two groups. CONCLUSION: Patients with DiLL (+) and DiLL (-) showed different clinical courses depending on VP severity at the non-fused discs after single-level TLIF.

Oxygen-glucose deprivation-induced glial cell reactivity in the rat primary neuron-glia co-culture.

It has been demonstrated that in vivo brain ischemia induces activation and proliferation of astrocytes and microglia. However, the mechanism underlying the ischemia-induced activation and proliferation of these cells remains to be unclear. Oxygen-glucose deprivation (OGD), an in vitro ischemia mimic, has been extensively used to analyze the hypoxia response of various cell types. This study examined the OGD-induced changes in the expression level of astrocytes and microglia marker proteins and immunoreactivity for Ki-67, a marker protein for cell proliferation, using rat primary hippocampal neuron-glia co-culture (NGC) cells. Furthermore, OGD-induced changes in the expression of M1/M2 microglia phenotype-related genes were also examined. MTT assay indicated that 120 min of OGD decreased cell viability, and immunocytochemistry indicated that 120 min of OGD abolished most microtubule-associated protein 2 (MAP2)-immunopositive neurons. In contrast, glial fibrillary acidic protein (GFAP)-immunopositive astrocytes and ionized calcium-binding adapter protein-1 (Iba-1)-immunopositive microglia, and 2',3'-cyclic nucleotide-3'-phosphodiesterase (CNPase)-immunopositive oligodendrocytes survived OGD. Western blot assays and double-immunofluorescent staining indicated that OGD increased the GFAP expression level and the Ki-67-immunopositive/GFAP-immunopositive cells' ratio. Real-time PCR analysis showed that OGD altered M1 microglia phenotype-related genes. Specifically, OGD decreased the expression level of CD32 and interleukin-1ß (IL-1ß) genes and increased that of the inducible nitric oxide synthase (iNOS) gene. Therefore, applying OGD to NGC cells could serve as a useful in vitro tool to elucidate the molecular mechanisms underlying brain ischemia-induced changes in GFAP expression, astrocyte proliferation, and M1 microglia phenotype-related gene expression.

Effect of Preoperative Severity and Location of Lumbar Intervertebral Disc Vacuum Phenomenon on Surgical Outcomes After Single-Level Transforaminal Lumbar Interbody Fusion.

OBJECTIVE: This study aimed to examine whether preoperative severity and location of lumbar intervertebral disc vacuum phenomenon (VP) influence surgical outcomes after single-level transforaminal lumbar interbody fusion. METHODS: We included 106 patients (age, 67.4 ± 10.4 years; 51 male/55 female) with lumbar degenerative diseases, who were treated with single-level transforaminal lumbar interbody fusion. Severity of VP (SVP) score was measured preoperatively. SVP score at fused disc was used as SVP (FS) score and at nonfused discs was used as SVP (non-FS) score. Surgical outcomes were assessed using the Oswestry Disability Index (ODI) and visual analog scale (VAS; low back pain (LBP), lower extremity pain, numbness, LBP in motion, in standing, and in sitting). The patients were divided into severe VP (FS or non-FS) and mild VP (FS or non-FS) groups, and surgical outcomes were compared between the 2 groups. Correlations between each SVP score and surgical outcomes were analyzed. RESULTS: There were no differences in surgical outcomes between the severe VP (FS) and mild VP (FS) groups. Postoperative ODI, VAS score for LBP, lower extremity pain, numbness, and LBP in standing were significantly worse in the severe VP (non-FS) group than in the mild VP (non-FS) group. SVP (non-FS) scores significantly correlated with postoperative ODI, VAS score for LBP, lower extremity pain, numbness, and LBP in standing; however, SVP (FS) scores did not correlate with any surgical outcomes. CONCLUSIONS: Preoperative SVP at fused disc is not associated with surgical outcomes; however, SVP at nonfused discs is correlated with clinical outcomes.

[Single-laboratory Validation Study and Surveillance Using an Improved Multiresidue Analytical Method for Veterinary Drugs in Livestock Products by LC-MS/MS].

A method for the rapid analysis of multiclass residual veterinary drugs in poultry muscle, egg, and raw milk was validated in accordance with Japanese guidelines. Using LC-MS/MS, 20 veterinary drugs, including sulfonamides, coccidiostats, and macrolides were analyzed in one injection. Analytes were extracted from the samples with acetonitrile and then dehydrated and salted out using magnesium sulfate, trisodium citrate, and sodium chloride. This method was assessed by performing recovery tests of chicken muscle, duck muscle, egg, and raw milk spiked with 20 new target analytes at concentrations of 10 and 100 µg/kg. According to this method, 17 out of 20 target analytes satisfied the guideline criteria in chicken muscle and duck muscle, and all 20 target analytes met the criteria in egg and raw milk. The limit of quantification was less than MRLs for all analytes. Residues were detected in 4 out of 99 samples and analyzed using the validated method, finding that the levels of all residues were lower than the limits of quantification. These results suggest that continuous monitoring for a new trend of veterinary drugs is necessary.

Enhanced mitochondrial oxidative metabolism in peripheral blood mononuclear cells is associated with fatty liver in obese young adults.

Systemic inflammation underlies the association between obesity and nonalcoholic fatty liver disease (NAFLD). Here, we investigated functional changes in leukocytes' mitochondria in obese individuals and their associations with NAFLD. We analyzed 14 obese male Japanese university students whose body mass index was > 30 kg/m2 and 15 healthy age- and sex-matched lean university students as controls. We observed that the mitochondrial oxidative phosphorylation (OXPHOS) capacity with complex I + II-linked substrates in peripheral blood mononuclear cells (PBMCs), which was measured using a high-resolution respirometry, was significantly higher in the obese group versus the controls. The PBMCs' mitochondrial complex IV capacity was also higher in the obese subjects. All of the obese subjects had hepatic steatosis defined by a fatty liver index (FLI) score ≥ 60, and there was a positive correlation between their FLI scores and their PBMCs' mitochondrial OXPHOS capacity. The increased PBMCs' mitochondrial OXPHOS capacity was associated with insulin resistance, systemic inflammation, and higher serum levels of interleukin-6 in the entire series of subjects. Our results suggest that the mitochondrial respiratory capacity is increased in the PBMCs at the early stage of obesity, and the enhanced PBMCs' mitochondrial oxidative metabolism is associated with hepatic steatosis in obese young adults.

Aiming for dynamic behaviours of molecular metal chains.

The dynamical functions of molecular metal chains, that could be derived from unique physical and chemical properties coupled with self-assembly of metal chain components, have largely been unexplored, and this review paper focuses on the dynamic behaviours of Pd chains supported by linear tetraphosphines, meso- and rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 recently reported, and the current development on fine-tuning of metal chains by introducing heterometal atoms, i.e. heterometallic molecular metal chains, that are considered as promising dynamical components in the next generation.

Postoperative change in lumbopelvic alignment after short-segment transforaminal lumbar interbody fusion is related to preoperative postural difference in lumbar lordosis.

BACKGROUND: Postoperative changes in lumbar lordosis (LL) after transforaminal lumbar interbody fusion (TLIF) and the related factors are not well-understood. Recently, the preoperative difference in LL between standing and supine positions (DiLL) was proposed as a factor for predicting postoperative radiologic outcomes after short-segment TLIF. This study investigated the influence of DiLL on mid-term radiological outcomes after short-segment TLIF. METHODS: Sixty-six patients with lumbar degenerative disease treated with short-segment TLIF (1-2 levels) who underwent lumbar spine standing radiographs at 3 months, 6 months, 1 year, 2 years, 3 years, 4 years, and 5 years postoperatively were divided into DiLL (+) and DiLL (-) groups (preoperative DiLL ≥0° and <0°, respectively). Associations between the postoperative change in LL and DiLL and clinical outcomes (Oswestry disability index (ODI) and Nakai score) were evaluated. RESULTS: Temporary restoration of LL (+4.5°) until 1 year postoperatively and a subsequent decrease in LL from 1 to 5 years postoperatively (-5.3°) was observed in the DiLL (+) group. No postoperative change in LL was observed in the DiLL (-) group. Postoperative changes in LL were mainly observed in non-fused segments. The postoperative change in LL (ΔLL) until 1 year postoperatively had a significant positive association with DiLL (p = 0.00028), whereas ΔLL from 1 to 5 years postoperatively showed a significant negative association with DiLL (p = 0.010) and a positive association with Nakai score (p = 0.028). ΔLL until 5 years postoperatively showed a significant positive association with postoperative ODI improvement (p = 0.011). CONCLUSIONS: DiLL (+) patients showed a specific time course with temporary LL restoration until 1 year postoperatively and a subsequent decrease in LL from 1 to 5 years postoperatively. Patients with larger postoperative increase in LL until 5 years postoperatively and lesser decrease in LL from 1 to 5 years postoperatively tended to show better mid-term clinical outcomes.

[Simultaneous Determination of Pesticide Residues in Brown Rice Using GC-MS/MS and LC-MS/MS].

This study developed a method that simultaneously detected 283 pesticide residues in brown rice using GC-MS/MS and LC-MS/MS. In this method, we examined the desirable amount of sodium chloride required for salting out and the SPE cartridge required for clean-up. Pesticide residues from the sample were extracted with acetonitrile using a homogenizer and mixed with salts including anhydrous magnesium, two types of citrate, and sodium chloride. The sample solution of the acetonitrile layer was cleaned up using the GCB/NH2 (200 mg/200 mg, 6 mL) SPE cartridge. The determination method was validated using two concentrations (0.01 and 0.1 µg/g) of 283 pesticides based on the validation guideline of the Ministry of Health, Labor and Welfare in Japan. Of the 283 pesticides, 250 were detected satisfactorily. In addition, 59 brown rice samples sold in Tokyo were surveyed using the same method. Out of 44 samples, 12 pesticide residues below MRLs were detected. Therefore, this developed method is useful for the simultaneous determination of pesticide residues in brown rice.

Comparison of pain and discomfort in supine and lateral positions after surgery for lumbar degenerative disease: A prospective randomized controlled study.

INTRODUCTION: To compare postoperative pain and discomfort between supine and lateral positions after lumbar surgery, a prospective randomized controlled study was performed. METHODS: Forty-three patients with lumbar degenerative disease, treated by decompression (n = 23) or fusion surgery (n = 20), were randomly assigned to be placed in either the supine (supine group: n = 21) or lateral (lateral group: n = 22) position postoperatively, and asked to maintain their position until a day after the surgery. Postoperative back pain and discomfort (visual analog scale [VAS], 0-100 mm) and the number of patients who could maintain their position were examined. RESULTS: The VAS scores for back pain (supine: 64.9 ± 22.0, lateral: 55.7 ± 21.4) showed no significant difference between the positions. However, the supine group showed significantly more severe discomfort (75.6 ± 15.7) than the lateral group (64.9 ± 15.7, p = 0.039). Significantly fewer patients maintained their position in the supine group (28.2%) than in the lateral group (68.2%; p = 0.022). Among patients who underwent fusion surgery, significantly fewer patients maintained their position in the supine group (10.0%) than those in the lateral group (60.0%, p = 0.029). CONCLUSION: Postoperative discomfort was significantly reduced in the lateral position than in the supine position; thus, the lateral position is more suitable after lumbar surgery in terms of postoperative discomfort.

Changes in lumbar lordosis and predicted minimum 5-year surgical outcomes after short-segment transforaminal lumbar interbody fusion.

Although most patients who undergo transforaminal lumbar interbody fusion (TLIF) show favorable surgical results, some still have unfavorable results for various reasons. This study aimed to investigate the influence of differences in lumbar lordosis (LL) between the standing and supine positions (DiLL: supine LL-standing LL) on minimum 5-year surgical outcomes after short-segment TLIF. Ninety-one patients with lumbar degenerative disease who underwent short-segment TLIF (1-2 levels) were categorized based on preoperative differences in LL as DiLL (+) and DiLL (-). Comparison and correlation analyses were performed. The incidence of adjacent segment disease (ASD) by radiology (R-ASD) and symptomatic ASD (S-ASD), bony fusion rates, and pre- and postoperative clinical scores (visual analog scale [VAS]; Japanese Orthopaedic Association [JOA] score; Oswestry disability index (ODI); and Nakai's score) were evaluated. Postoperatively, VAS for low back pain (LBP) in the sitting position, JOA scores for LBP, lower leg pain, intermittent claudication, ODI, and Nakai's score were significantly worse in the DiLL (+) group than in the DiLL (-) group. DiLL values were significantly correlated with VAS for LBP, ODI, and Nakai's score, postoperatively. Positive DiLL values were associated with poorer postoperative outcomes. DiLL is a simple and useful method for predicting mid-term outcomes after TLIF.

The expression and phosphorylation of SMAD3 protein in microglia and astrocytes of the rat hippocampus after transient global cerebral ischemia.

SMAD3 protein transduces signals from TGF-ß and activins. In vitro studies have shown that SMAD3 plays an important role in regulating of micoglia and astrocytic function. However, there is little information on the association between SMAD3 signaling and the pathophysiology of the glial cells in the post-ischemic hippocampus. In this study, we examined the time-course changes in the expression and phosphorylation of SMAD3 in the rat hippocampus using a rat model of global cerebral ischemia. Most pyramidal neuronal cells in the CA1 region died within 7 days after ischemia. The number of SMAD3- or phosphorylated SMAD3 (p-SMAD3)-immunopositive microglia or astrocytes increased in the CA1 region 7 days after ischemia. Real-time PCR analysis showed an increase in the level of TGF-ß1 mRNA in the hippocampus after ischemia. Intracerebroventricular injection of SB525334, a selective inhibitor of TGF-ß receptor I kinase (ALK5), reduced the ischemia-induced p-SMAD3 immunoreactivity in the microglia and astrocytes. By contrast, intracerebroventricular injection of SB525334 did not affect the ischemia-induced neuronal cell death. These results suggest that ischemia-induced SMAD3 phosphorylation in the microglia and astrocytes of post-ischemic hippocampi is associated with tissue repair and not neuroprotection.

Empagliflozin improves cardiac mitochondrial function and survival through energy regulation in a murine model of heart failure.

BACKGROUND: Sodium-glucose cotransporter 2 (SGLT2) inhibitors have been demonstrated to have beneficial effects on HF in large clinical trials; however, the mechanisms remain to be elucidated. The aim of this study was to clarify the mechanisms by which empagliflozin, one of SGLT2 inhibitors, affects heart failure. METHOD AND RESULTS: Eight-week-old male mice deficient for heart and skeletal muscle-specific manganese superoxide dismutase (MnSOD-cKO mice), a murine model of dilated cardiomyopathy, were given food mixed with or without 10 mg/kg empagliflozin for 7 weeks and evaluated. Both the survival rate and cardiac fibrosis were significantly improved in the empagliflozin group. The capacity for oxidative phosphorylation in cardiac mitochondria was significantly upregulated as measured with Oxygraph-2k respirometer, and blood lactate levels produced by anaerobic metabolism were significantly lower in the empagliflozin group. Energy expenditure was significantly improved in the empagliflozin group, measured by respiratory gas analysis, with a concomitant reduction in serum leptin concentration and increase in food intake. A moderate amount of glucose was excreted in urine in the empagliflozin group; however, the available energy substrate in the body nonetheless expanded because of the much higher caloric intake. CONCLUSIONS: We conclude that empagliflozin improved cardiac mitochondrial function and upregulated energy metabolism even in HF in mice. These findings provide novel mechanisms for the beneficial effects of SGLT2 inhibitors on HF.

Unexpectedly rapid decrease in the size of a spinal epidural abscess after percutaneous posterior pedicle screw fixation without decompression surgery: a case report.

INTRODUCTION: Spondylodiscitis accompanying spinal epidural abscess is often treated with decompression surgery when there are neurological symptoms. We report a case of spondylodiscitis accompanying spinal epidural abscess with severe lower extremity pain that was successfully treated with percutaneous posterior pedicle screw fixation without decompression surgery. CASE PRESENTATION: A 53-year-old man was admitted to our hospital with severe low back pain (LBP), lower extremity pain and numbness, and fever. Lumbar magnetic resonance imaging (MRI) revealed spondylodiscitis at L2-L3 and a small epidural abscess located ventrally in the spinal canal. Initially, the patient was treated conservatively with empirical antibiotics. However, the lower extremity symptoms worsened and the epidural abscess expanded cranially to the T12 level. Percutaneous pedicle screw fixation without decompression was performed thirty-three days after admission. Postoperatively, the LBP and lower extremity pain dramatically improved. A postoperative MRI performed one week post-operatively showed an unexpectedly rapid decrease in the size of the epidural abscess, although no decompression surgery was performed. Two months after surgery, the epidural abscess completely disappeared. At the final follow-up (five years postoperatively), no recurrence of epidural abscess was observed, and the patient had no symptoms or disturbance of activities of daily living. DISCUSSION: This surgical strategy should be carefully selected for patients with spondylodiscitis with accompanying spinal epidural abscess who have lower extremity symptoms. The stabilising effect of pedicle screw fixation may be advantageous for controlling spinal infections. Percutaneous posterior pedicle screw fixation without decompression is an optional treatment for spondylodiscitis accompanying spinal epidural abscess.

Prediction of anatomically and biomechanically feasible precision grip posture of the human hand based on minimization of muscle effort.

We developed a method to estimate a biomechanically feasible precision grip posture of the human hand for a given object based on a minimization of the muscle effort. The hand musculoskeletal model was constructed as a chain of 21 rigid links with 37 intrinsic and extrinsic muscles. To grasp an object, the static force and moment equilibrium condition of the object, force balance between the muscle and fingertip forces, and static frictional conditions must be satisfied. We calculated the hand posture, fingertip forces, and muscle activation signals for a given object to minimize the square sum of the muscle activations while satisfying the above kinetic constraints using an evolutionary optimization technique. To evaluate the estimated hand posture and fingertip forces, a wireless fingertip force-sensing device with two six-axis load cells was developed. When grasping the object, the fingertip forces and hand posture were experimentally measured to compare with the corresponding estimated values. The estimated hand postures and fingertip forces were in reasonable agreement to the corresponding measured data, indicating that the proposed hand posture estimation method based on the minimization of muscle effort is effective for the virtual ergonomic assessment of a handheld product.

[Surveillance of Acaricides in Honey].

By using the LC-MS/MS method developed by us, we determined the residual amounts of acaricides in honey samples commercially available in Tokyo from April 2015 to March 2021. The results of analyzing 127 honey samples, amitraz was detected in 85 samples at the level of 1.1-34.1 µg/kg. Propargite was detected in 3 samples at 2.4-3.8 µg/kg. None of them was beyond the Japanese MRLs or uniform limits. In these survey for 6 years, amitraz was detected in high rate throughout the year. But, the present results imply that amitraz has been used properly in actual bee-keeping because of no violation of MRL and less fluctuation in the detected levels. On the other hand, propargite was detected at the levels over LOQ in domestic honey samples for the first time in 2020, which may suggest a new trend of acaricide use in apiculture in Japan.

Postoperative loss of correction after combined posterior and anterior spinal fusion surgeries in a lumbar burst fracture patient with Class II obesity.

Background: When treating thoracolumbar fractures with severe cranial endplate injury but no or slight caudal endplate injury, it is debatable whether anterior fusion should be performed only for the injured cranial level, or for both cranial and caudal levels. We report an unexpected postoperative correction loss after combined multilevel posterior and single-level anterior fusion surgery in a patient with obesity. Case Description: A 28-year-old male with Class II obesity was brought to the emergency room with an L1 burst fracture with spinal canal involvement. Cranial endplate injury was severe, whereas caudal endplate injury was mild. The first surgery with 1-above 1-below posterior fixation failed to achieve sufficient stability; thus, additional surgeries (3-above 3-below posterior fixation and single-level T12-L1 anterior fusion) were performed. Postoperatively, the local kyphosis angle (LKA) between T12 and L2 was 22° in the lateral lying position and 29° in the standing position. Twenty-one-month post surgery, bony fusion between T12 and L1 was observed, and the LKA was 28° in both the lateral lying and standing positions. After posterior implants were removed 24 months after the surgery, significant correction loss both at the T12-L1 segment (6°) and L1-L2 segment (6°) occurred, and LKA was 40° at the final follow-up. Conclusion: In this patient, an intense axial load due to excessive body weight was at least one of the causes of postoperative correction loss. Postural differences in LKA may be useful to evaluate the stability of thoracolumbar fractures after fusion surgery and to predict postoperative correction loss.

Effects of the difference between lumbar lordosis in the supine and standing positions on the clinical outcomes of decompression surgery for lumbar spinal stenosis.

OBJECTIVE: The authors sought to evaluate the relationship between the difference in lumbar lordosis (DiLL) in the preoperative supine and standing positions and spinal sagittal alignment in patients with lumbar spinal stenosis (LSS) and to determine whether this difference affects the clinical outcome of laminectomy. METHODS: Sixty patients who underwent single-level unilateral laminectomy for bilateral decompression of LSS were evaluated. Spinopelvic parameters in the supine and standing positions were measured preoperatively and at 3 months and 2 years postoperatively. DiLL between the supine and standing positions was determined as follows: DiLL = supine LL - standing LL. On the basis of this determination patients were then categorized into DiLL(+) and DiLL(-) groups. The relationship between DiLL and preoperative spinopelvic parameters was evaluated using Pearson's correlation coefficient. In addition, clinical outcomes such as visual analog scale (VAS) and Oswestry Disability Index (ODI) scores between the two groups were measured, and their relationship to DiLL was evaluated using two-group comparison and multivariate analysis. RESULTS: There were 31 patients in the DiLL(+) group and 29 in the DiLL(-) group. DiLL was not associated with supine LL but was strongly correlated with standing LL and pelvic incidence (PI) - LL (PI - LL). In the preoperative spinopelvic alignment, LL and SS in the standing position were significantly smaller in the DiLL(+) group than in the DiLL(-) group, and PI - LL was significantly higher in the DiLL(+) group than in the DiLL(-) group. There was no difference in the clinical outcomes 3 months postoperatively, but low-back pain, especially in the sitting position, was significantly higher in the DiLL(+) group 2 years postoperatively. DiLL was associated with low-back pain in the sitting position, which was likely to persist in the DiLL(+) group postoperatively. CONCLUSIONS: We evaluated the relationship between DiLL and spinal sagittal alignment and the influence of DiLL on postoperative outcomes in patients with LSS. DiLL was strongly correlated with PI - LL, and in the DiLL(+) group, postoperative low-back pain relapsed. DiLL can be useful as a new spinal alignment evaluation method that supports the conventional spinal sagittal alignment evaluation.

Unsymmetric Dinuclear RhI2 and RhIRhIII Complexes Supported by Tetraphosphine Ligands and Their Reactivity of Oxidative Protonation and Reductive Dechlorination.

Two linear tetradentate phosphine ligands, meso-Ph2PCH2P(Ph)CH2XCH2P(Ph)CH2PPh2 (X = CH2 (meso-dpmppp), NBn (meso-dpmppmNBn; Bn = benzyl)) were utilized to synthesize unsymmetrical dinuclear RhI complexes, [Rh2Cl2(meso-dpmppp)(L)] (L = XylNC (1a), CO (1b)) and [Rh2Cl2(meso-dpmppmNBn)(L)] (L = XylNC (1c), CO (1d)), where electron-deficient RhI → RhI centers with 30 valence electrons are supported by a tetraphosphine in an unusual cis-/trans-P,P coordination mode. The RhI dimers of 1a-d were treated with HCl under air to afford the RhI → RhIII dimers with 32 e-, [Rh2Cl4(meso-dpmppp)(L)] (L = XylNC (4a), CO (4b)) and [Rh2Cl4(meso-dpmppmNBn)(L)] (L = XylNC (4c), CO (4d)), via intermediate hydride complexes, [{RhCl2(µ-H)RhCl(L)}(meso-dpmppp)] (L = XylNC (2a), CO (2b)) and [{RhCl2(µ-H)RhCl(L)}(meso-dpmppmNBn)] (L = XylNC (2c), CO (2d)), and [{Rh(H)Cl2(µ-Cl)Rh(L)}(meso-dpmppp)] (L = XylNC (3a), CO (3b)) and [{Rh(H)Cl2(µ-Cl)Rh(L)}(meso-dpmppmNBn)] (L = XylNC (3c), CO (3d)). The hydride intermediates 2 and 3 were monitored under nitrogen by 1H{31P} and 31P{1H} NMR techniques to reveal two reaction pathways depending on the terminal auxiliary ligand L. Further, the reductive dechlorination converting RhIRhIII (4b,d) to RhI2 (1b,d) was accomplished with a CO terminal ligand by reacting with various amines that acted as one-electron reducing agents through an inner-sphere electron transfer mechanism. DFT calculations were performed to elucidate the electronic structures of 1a-d and 4a-d and to estimate the structures of the hydride intermediate complexes 2 and 3.