The medial gap is a reliable indicator for intraoperative soft tissue balancing in posterior-stabilized total knee arthroplasty.

BACKGROUND: Appropriate soft tissue balance and accurate alignment are important for successful total knee arthroplasty (TKA). However, the optimal technique for establishing and measuring soft tissue balancing remains unclear. The aim of this study was to analyze the intraoperative medial and lateral gap pattern using digital knee balancer in posterior-stabilized (PS) TKA. METHODS: This study involved 55 patients with medial osteoarthritis who underwent a primary TKA using an image-free navigation system. The extension gap and the flexion gap at 90° knee flexion were assessed using an offset seesaw-type digital balancer. Continuous joint distraction force from 10 lb to 60 lb was applied. Medial gap, lateral gap, and varus angle were measured. RESULTS: The medial bone gap difference between extension and flexion was constant regardless of the distraction force from 20 lb to 60 lb. The lateral bone gap was significantly greater than the medial bone gap in extension and flexion from 30 lb to 60 lb (P < 0.05). The varus angle changed depending on the distraction force, especially in flexion. The varus angle in flexion was significantly greater than that in extension from 40 lb to 60 lb (P < 0.05). CONCLUSIONS: The medial bone gap is a reliable indicator unaffected by the distraction force during surgery and is useful for adjusting the medial gap in extension and flexion appropriately to ensure medial stability in PS-TKA. The digital knee balancer and navigation system support both precise gap assessment and surgery.

High Excess Risk of Heart Disease Mortality among Hiroshima Atomic Bomb Male Survivors Exposed Near the Hypocenter.

Heart disease (HD) mortality is the second leading cause of death in Japan. The HD mortality risk among Atomic bomb survivors is slightly positive but shows a statistically significant dose-response relationship with initial radiation dose, as reported by the Radiation Effects Research Foundation. In that report, dosimetry was based on initial radiation only, with the effect of indirect radiation dose not taken into consideration. The atomic bomb radiation, however, consisted of both initial and residual radiation. We reevaluated the dose-response relationship for HD mortality using exposure distance (ground distance between the location where exposed and the hypocenter) as a surrogate indicator of radiation dose. At Hiroshima University, a cohort study has been conducted with Hiroshima Atomic Bomb Survivors (ABS) since 1970. We selected 29605 subjects from the ABS who were exposed at 3.5 km or less from the hypocenter and alive on January 1, 1970. These subjects, referred to as "Hiroshima hibakusha" in this paper, were followed until December 31, 2010. We stratified the cohort data with respect to sex and age at the time of bombing (ATB) into 10-year age groups. For each stratum, by applying an extended Cox regression model with time-dependent covariates, we analyzed the risk of HD mortality using either initial radiation dose or exposure distance as an explanatory variable. The results indicate a high excess risk in males and older age ATB females who were exposed near the hypocenter. This difference may be explained by the effect of female sex hormone on the circulatory system among young age ATB females. Some unknown risk factor related to exposure distance was also implicated in the elevated risk of HD among the Hiroshima hibakusha, especially in males. This necessitates further study.

In vivo kinematic analysis of posterior-stabilized total knee arthroplasty for the valgus knee operated by the gap-balancing technique.

BACKGROUND: Most in vivo kinematic studies of total knee arthroplasty (TKA) report on the varus knee. The objective of the present study was to evaluate in vivo kinematics of a posterior-stabilized fixed-bearing TKA operated on a valgus knee during knee bending in weight-bearing (WB) and non-weight-bearing (NWB). METHODS: A total of sixteen valgus knees in 12 cases that underwent TKA with Scorpio NRG PS knee prosthesis and that were operated on using the gap balancing technique were evaluated. We evaluated the in vivo kinematics of the knee using fluoroscopy and femorotibial translation relative to the tibial tray using a 2-dimensional to 3-dimensional registration technique. RESULTS: The average flexion angle was 111.3°±7.5° in WB and 114.9° ± 8.4° in NWB. The femoral component demonstrated a mean external rotation of 5.9° ± 5.8° in WB and 7.4° ± 5.2° in NWB. In WB and NWB, the femoral component showed a medial pivot pattern from 0° to midflexion and a bicondylar rollback pattern from midflexion to full flexion. The medial condyle moved similarly in the WB condition and in the NWB condition. The lateral condyle moved posteriorly at a slightly earlier angle during the WB condition than during the NWB condition. CONCLUSIONS: We conclude that similar kinematics after TKA can be obtained with the gap balancing technique for the preoperative valgus deformity when compared to the kinematics of a normal knee, even though the magnitude of external rotation was small. LEVEL OF EVIDENCE: IV.

C-24 Stereochemistry of Marine Sterols: (22E)-25,28-Dimethyl- stigmasta-5,22,28-trien-3ß-ol and 25,28-Dimethylstigmasta-5,28-dien-3ß-ol.

The C-24 configurations of (22E)-25,28-dimethylstigmasta-5,22,28-trien-3ß-ol (1) and 25,28-dimethylstigmasta-5,28-dien-3ß-ol (2), isolated from the sponge Topsentia ophiraphidites in our previous work, were determined to be both S, through the synthesis of stereodefined (24S)- and (24R)-epimers of 1 and 2 and comparison of the 1H and 13C NMR spectroscopic data. In addition, the C-24 configurations of the marine sterols having the same structures as 1 and 2 and their derivatives were also assigned for the first time by NMR comparison.

Enantioselective synthesis of AG-041R by using N-heteroarenesulfonyl cinchona alkaloid amides as organocatalysts.

The organocatalytic enantioselective decarboxylative addition of malonic acid half thioesters to ketimines derived from isatins by using N-heteroarenesulfonyl cinchona alkaloid amides afforded products with high enantioselectivity. The products could be converted into optically active AG-041R. X-ray crystallographic analysis revealed that the hydrogen bonding between the sulfonimide proton and the 8-quinolyl nitrogen atom plays an important role in exerting the enantioselectivity of the reaction.

Phenolic constituents from the fruit juice of Flacourtia inermis.

A chemical investigation of the fruit juice of Flacourtia inermis furnished five caffeoylquinic acid derivatives: methyl chlorogenate (1), methyl 5-O-caffeoylquinate (2), methyl 4-O-caffeoylquinate (3), n-butyl chlorogenate (4), n-butyl 5-O-caffeoylquinate (5) and a rare phenolic glucoside (rel)-6α-benzoyloxy-1α,2α-dihydroxy-5-oxocyclohex-3-enecarboxylic acid 2-(6-O-benzoyl-ß-D-glucopyranosyloxy)-5-hydroxybenzyl ester (6), together with quinic acid (7) and malic acid (8). Compounds 1, 2, 4 and 5 showed strong radical scavenging properties towards the 2,2'-diphenyl-1-picrylhydrazyl radical.

N-(heteroarenesulfonyl)prolinamides-catalyzed aldol reaction between acetone and aryl trihalomethyl ketones.

Enantiomerically enriched trihalomethyl-substituted alcohols having a quaternary chiral carbon center can be prepared by the catalytic enantioselective cross-aldol reaction of acetone with trihalomethyl ketones by using N-(8-quinolinesulfonyl)prolinamide as an organocatalyst. The MO calculations elucidate that the hydrogen bonding between the sulfonimide proton and the 8-quinolyl nitrogen atom plays an important role in exerting the enantioselectivity of the reaction.

Fatty acid derivatives and dammarane triterpenes from the glandular trichome exudates of Ibicella lutea and Proboscidea louisiana.

Ibicellalutea and Proboscidea louisiana, both of the Martyniaceae family, are known for rich glandular trichomes on their leaves and stems. Chemical investigations of the glandular trichome exudates on leaves of the two plants furnished three types of secondary metabolites, glycosylated fatty acids, glycerides (2-O-(3,6-diacetyloxyfattyacyl)glycerols and 2-O-(3-acetyloxyfattyacyl)glycerols) and dammarane triterpenes. The glycosylated fatty acids from I. lutea were determined to be 6(S)-(6-O-acetyl-beta-D-glucopyranosyloxy)-octadecanoic acid (1A), -eicosanoic acid (1B) and -docosanoic acid (1C), as well as their respective deacetyl congeners (2A, 2B and 2C), whereas P. louisiana furnished 8(S)-(6-O-acetyl-beta-D-glucopyranosyloxy)-eicosanoic acid (3A) and -docosanoic acid (3B) and their respective deacetyl congeners (4A and 4B), together with 2B. Both plants contained 12 identical 2-O-[(3R,6S)-3,6-diacetyloxyfattyacyl]glycerols (5A-L), in which the fatty acyl moieties contained between 17 and 21 carbon atoms. The corresponding mono-acetyloxy compounds, 2-O-[(3R)-3-acetyloxyfattyacyl]glycerols (6A-L) were detected in both plants. Among these glycerides, ten compounds (5A, 5C, 5F, 5H, 5K, 6A, 6C, 6F, 6H and 6K) had iso-fattyacyl structures and four (5E, 5J, 6E and 6J) had anteiso-fattyacyl structures. A previously unknown dammarane triterpene, betulatriterpene C 3-acetate (7), was isolated together with three known dammarane triterpenes, 24-epi-polacandrin 1,3-diacetate (8), betulatriterpene C (9) and 24-epi-polacandrin 3-acetate (10) from I. lutea, whereas 12 dammarane triterpenes, named probosciderols A-L (12-23), and the known compound betulafolienetriol (11) were isolated from P. louisiana. The structures of these compounds were elucidated by spectroscopic analysis including 2D-NMR techniques and chemical transformations. The 6-O-acetylglucosyloxy-fatty acids 1A-C (42%) and the dammarane triterpenes 7-10 (31%) were the two most abundant constituents in the glandular trichome exudate of I. lutea, whereas the dammarane triterpenes 11-23 (47%) and the glucosyloxy-fatty acids (4A, 4B and 2B) (38%) were the most abundant constituents in the glandular trichome exudate of P. louisiana.

Geranylated flavanones from the secretion on the surface of the immature fruits of Paulownia tomentosa.

Chemical investigation of the methanol extract of the viscous secretion on the surface of immature fruits of Paulownia tomentosa furnished nine geranylated flavanones, 6-geranyl-5,7-dihydroxy-3',4'-dimethoxyflavanone (1), 6-geranyl-3',5,7-trihydroxy-4'-methoxyflavanone (2), 6-geranyl-4',5,7-trihydroxy-3',5'-dimethoxyflavanone (3), 6-geranyl-4',5,5',7-tetrahydroxy-3'-methoxyflavanone (4), 6-geranyl-3,3',5,7-tetrahydroxy-4'-methoxyflavanone (5), 4',5,5',7-tetrahydroxy-6-[6-hydroxy-3,7-dimethyl-2(E),7-octadienyl]-3'-methoxyflavanone (6), 3,3',4',5,7-pentahydroxy-6-[6-hydroxy-3,7-dimethyl-2(E),7-octadienyl]flavanone (7), 3,3',4',5,7-pentahydroxy-6-[7-hydroxy-3,7-dimethyl-2(E)-octenyl]flavanone (8), and 3,4',5,5',7-pentahydroxy-3'-methoxy-6-(3-methyl-2-butenyl)flavanone (9), along with six known geranylated flavanones. Among these, compounds 4, 6-9 and the known 6-geranyl-3',4',5,7-tetraahydroxyflavanone (diplacone), 6-geranyl-3,3',4',5,7-pentahydroxyflavanone (diplacol) and 3',4',5,7-pentahydroxy-6-[7-hydroxy-3,7-dimethyl-2(E)-octenyl]flavanone showed potent radical scavenging effects towards DPPH radicals.

Molecular cloning of ecdysone 20-hydroxylase and expression pattern of the enzyme during embryonic development of silkworm Bombyx mori.

In various insects, 20-hydroxyecdysone (20E) is indispensable for embryonic development. In eggs of the silkworm Bombyx mori, 20E has been demonstrated to be produced by two metabolic pathways: de novo synthesis from cholesterol and dephosphorylation of ovary-derived physiologically inactive ecdysteroid phosphates. In the former, ecdysone 20-hydroxylase (E20OHase) has been suggested to be a key enzyme. In the latter, it has been demonstrated that the dephosphorylation of ecdysteroid phosphates is catalyzed by a specific enzyme, ecdysteroid-phosphate phosphatase (EPPase). In this study, a cDNA encoding E20OHase was cloned from 3-day-old nondiapause eggs of B. mori and sequenced using PCR techniques. The protein exhibited the signature sequences characteristic of P450 enzymes, and mediated the conversion of ecdysone to 20E using the baculovirus expression system. Semi-quantitative analysis revealed that the E20OHase mRNA is expressed predominantly during gastrulation and organogenesis in nondiapause eggs, but is scarcely detected in diapause eggs whose development is arrested at the late gastrula stage. The developmental changes in the expression patterns of E20OHase and EPPase suggest that both enzyme activities are regulated at the transcription level, and both enzymes contribute cooperatively to 20E formation during embryonic development.

C-24 stereochemistry of marine sterols: (22E)-24-(isopropenyl)-22-dehydrocholesterol and 24-isopropenylcholesterol.

The C-24 configuration of (22E,24xi)-24-isopropenyl-22-dehydrocholesterol (1), which was recently isolated from the Colombian Caribbean sponge, Topsentia ophiraphidites, was investigated. Synthesis of the stereodefined (24R)- and (24S)-(22E)-24-isopropenyl-22-dehydrocholesterols (1a, 1b) followed by (1)H- and (13)C-NMR data comparison of these sterols established the (24R)-configuration of 1. In addition, (24R)- and (24S)-24-isopropenylcholesterols (2a and 2b) were also synthesized and their NMR data are provided. The C-24 configurations of the samples of 24-isopropenylcholesterol reported previously are discussed.

Geranylated phenolic constituents from the fruits of Artocarpus nobilis.

Chemical investigation of the combined dichloromethane and ethyl acetate extracts of the fruits of Artocarpus nobilis, furnished four new geranylated phenolic constituents, 2,4,4'-trihydroxy-3-[(2E)-5-methoxy-3,7-dimethylocta-2,6-dienyl]chalcone (4), 1-(3,4-dihydro-3,5-dihydroxy-2-methyl-2-(3-methyl-2-butenyl)-2H-1-benzopyran-6-yl-3-(4-hydroxyphenyl)-2(E)-propen-1-one (5), 8-geranyl-3',4',7-trihydroxyflavone (8), 3'-geranyl-4',5,7-trihydroxyflavanone (9), together with known related compounds, xanthoangelol (1), xanthoangelol B (2), 3-geranyl-2,3',4,4'-tetrahydroxychalcone (3), lespeol (6), 8-geranyl-4',7-dihydroxyflavanone (7), and isonymphaeol-B (10). Compounds 3, 8 and 10 showed strong antioxidant activity against DPPH radical by spectrophotometric method.

Hyosgerin, a new optically active coumarinolignan, from the seeds of Hyoscyamus niger.

Hyosgerin, a new optically active coumarinolignan, has been isolated and characterized along with three other coumarinolignans, venkatasin, cleomiscosin A and cleomiscosin B, from the seeds of Hyoscyamus niger L. The structure was determined on the basis of spectroscopic analysis and chemical conversion. The optical properties and absolute stereochemistry of these coumarinolignans have also been studied and discussed.

Metabolic conversion of 24-methyl-Delta25-cholesterol to 24-methylcholesterol in higher plants.

Feeding of chemically synthesized [27-13C]codisterol ([27-13C]2), [27-13C]24-epicodisterol ([27-13C]3), [23,24-2H2]codisterol ([23,24-2H2]2), and [26,27-2H6]24-methyldesmosterol ([26,27-2H6]8) to Oryza sativa cell cultures, followed by MS and NMR analysis of the biosynthesized dihydrobrassicasterol (9)/campesterol (10), revealed that both (24R)- and (24S)-epimers of 24-methyl-Delta25-cholesterol (2/3) were converted to 9 and 10 via the common intermediate 24-methyldesmosterol (8).

Cupaniol, a New branched polyprenol, from Cupania latifolia.

A new branched polyprenol, designated cupaniol, has been isolated from the methanol extract of the leaves of Cupania latifolia (Sapindaceae). The structure was determined to be (2E,6E,12E,16E)-3,7,13,17,21-pentamethyl-10-(1-methylethenyl)-2,6,12,16,20-docosapentaen-1-ol on the basis of spectral analysis and conversion to a known compound.

Champanones, yellow pigments from the seeds of champa (Campomanesia lineatifolia).

Chemical investigation of the methanol extract of the seeds of Campomanesia lineatifolia Ruiz and Pav. (Myrtaceae) led to the isolation of two new beta-triketone type compounds, named champanones A (1) and B (2), together with the known 2,3-dihydro-5-hydroxy-6,8,8-trimethyl-2-phenyl-4H-1-benzopyran-4,7(8H)-dione (champanone C) (3). The structures of 1 and 2 were determined to be 2,2,4,4-tetramethyl-6-(1-oxo-3-phenylprop-2-enyl) cyclohexane-1,3,5-trione (occurs as an enol form) and 2,2,4-trimethyl-6-(1-oxo-3-phenylprop-2-enyl)cyclohexane-1,3,5-trione (occurs as an enol form), respectively, by means of spectroscopic analysis. The three compounds showed mild antimicrobial activity.

Structure elucidation of cyasterone stereoisomers isolated from Cyathula officinalis.

Chemical investigation of ecdysteroidal constituents of the roots and stems of Cyathula officinalis led to the isolation of two cyasterone stereoisomers, 2 and 3, together with the known cyasterone 1. The structures of compounds 2 and 3 were determined to be 28-epi-cyasterone and 25-epi-28-epi-cyasterone, respectively, by means of spectroscopic analysis. X-Ray structures of 1 and 2 confirmed the 24S,25S,28R configuration for 1 and 24S,25S,28S for 2.

Geranyl chalcone derivatives with antifungal and radical scavenging properties from the leaves of Artocarpus nobilis.

Antifungal activity guided fractionation of the n-butanol extract from the methanol extract of the leaves of Artocarpus nobilis furnished 2',4',4-trihydroxy-3'-geranylchalcone (1), 2 ',4',4-trihydroxy-3'-[6-hydroxy-3,7-dimethyl-2(E),7-octadienyl]chalcone (2), 2',4',4-trihydroxy-3'-[2-hydroxy-7-methyl-3-methylene-6-octaenyl]chalcone (3), 2',3,4,4'-tetrahydroxy-3'-geranylchalcone (4), 2',3,4,4'-tetrahydroxy-3'-[6-hydroxy-3,7-dimethyl-2(E),7-octadienyl]chalcone (5). The chalcones 3 and 5 are new natural products whereas 1 and 2 are reported first time from the family Moraceae. All these compounds showed good fungicidal activity against Cladosporium cladosporioides and high radical scavenging activity towards the 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical in TLC bio-autography method.