Cyclotrimerization of phenylacetylene catalyzed by a cobalt half-sandwich complex embedded in an engineered variant of transmembrane protein FhuA.

An (η5-cyclopentadienyl)cobalt(i) complex was covalently incorporated into an engineered variant of the transmembrane protein ferric hydroxamate uptake protein component: A, FhuA ΔCVFtev, using a thiol-ene reaction. A CD spectrum shows the structural integrity of the biohybrid catalyst. MALDI-TOF of the segment containing the anchoring site for the cobalt complex Cys545 confirmed successful conjugation. This biohybrid catalyst catalyzed the cyclotrimerization of phenylacetylene to give a mixture of regioisomeric 1,2,4- and 1,3,5-triphenylbenzene in aqueous medium.

1,4-Dihydropyridyl complexes of magnesium: synthesis by pyridine insertion into the magnesium-silicon bond of triphenylsilyls and catalytic pyridine hydrofunctionalization.

Magnesium bis(triphenylsilyl) [Mg(SiPh3)2(THF)2]·THF (1) reacted with a stoichiometric amount of pyridine to give the magnesium 4-(triphenylsilyl)dihydropyridyl complex [Mg(NC5H5-4-SiPh3)2(THF)3] (2). Using an excess of pyridine, a mixture of magnesium dihydropyridyl [Mg(NC5H6)2(py)4] (3) and 4-(triphenylsilyl)pyridine was formed. Complex 3 underwent exchange with pyridine-d5 at 25 °C to give [Mg(NC5D5H-4)2(py-d5)4] (3-HD). Analogous reactions with Me3TACD-supported magnesium triphenylsilyls [(Me3TACD)Mg(SiPh3)] (4) and [(Me3TACD·AlEt3)Mg(SiPh3)] (6) ((Me3TACD)H = Me3[12]aneN4: 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane) with pyridine gave [(Me3TACD)Mg(NC5H5-4-SiPh3)] (5), [(Me3TACD·AlEt3)Mg(NC5H5-4-SiPh3)] (7) and a mixture of [(Me3TACD)Mg(NC5H6)] (8) and 4-(triphenylsilyl)pyridine. Complex 8 is also formed by reacting 3 with (Me3TACD)H and underwent exchange with pyridine-d5 at higher temperatures. The activation energy for the exchange is about 25 kJ mol-1 higher than that for the exchange reaction of 3 to 3-HD. Complexes 2, 3, 3-HD, 5, 7 and 8 were characterized by NMR spectroscopy and 3, 5 and 8 by single crystal structure analysis. Complex 3 was found to be slightly active in the hydrosilylation of pyridine using phenylsilane, whereas complex 8 showed no activity. Both complexes 3 and 8 were active in the hydroboration of pyridine with pinacolborane.

Formate complexes of titanium(iv) supported by a triamido-amine ligand.

The terminal formate complex [(OCHO)Ti(N3N)] (3) containing the trianionic triamido-amine ligand (Me3SiNCH2CH2)3N3- (N3N) was prepared via salt metathesis of [ClTi(N3N)] (1) with sodium formate or alternatively by treatment of the alkyl complex [nBuTi(N3N)] (2) with ammonium formate [HNEt3][OCHO]. Deprotonation of 3 with potassium hexamethyldisilazide gave a polymeric helical chain of the oxo complex {K[OTi(N3N)]}n (4). Reaction of 2 with the trityl salt [Ph3C][B(3,5-Cl2C6H3)4] or the Brønsted acid [HNEt3][B(C6F5)4] gave [(Et2O)Ti(N3N)][BR4] (6[BR4]·Et2O) with R = 3,5-Cl2C6H3 or C6F5. The diethyl ether ligand was easily replaced by other L-type donor ligands such as tetrahydrofuran, pyridine, and 4-dimethylaminopyridine to give 6[BR4]·L with L = thf, py, and dmap. Reaction of 6[BR4]·Et2O with a stoichiometric amount of CO2 gave the dimeric, dicationic bis(carbamate)-bridged complexes [Ti{N(CH2CH2NSiMe3)2(CH2CH2NSiMe3(µ-CO2-ηO:ηO'))}]2[BR4]2 (7[BR4]2) through insertion of one CO2 into one of the titanium-amido bonds. Addition of pyridine to 7[B(C6F5)4]2 formed the monomeric carbamate complex [(py)Ti{((O2C-κ2O,O')NSiMe3CH2CH2)N(CH2CH2NSiMe3)2}][B(C6F5)4] (8[B(C6F5)4]·py). The cationic formate-bridged species [(Ti(N3N))2(µ-OCHO-ηO:ηO')][BR4] (10[BR4]) readily formed when the terminal formate complex 3 was reacted with the cationic 6[BR4]. The reactivity of triamido-amine stabilized titanium(iv) complexes is shown to differ considerably from that of related titanium tris(anilide) complexes.

Molecular magnesium hydrides supported by an anionic triazacyclononane-type ligand.

Molecular magnesium hydride with a terminal metal-hydrogen bond [Mg(iPr2TACN·AliBu3)H]2 supported by a monoanionic TACN-type ligand (TACN = 1,4-di-isopropyl-1,4,7-triazacyclononane) rearranges to form the dinuclear magnesium hydride [Mg(iPr2TACN·AlHiBu2)(µ-H)]2, exhibiting a rare MgH-Al interaction.

Metatheases: artificial metalloproteins for olefin metathesis.

The incorporation of organometallic catalyst precursors in proteins results in so-called artificial metalloenzymes. The protein structure will control activity, selectivity and stability of the organometallic site in aqueous medium and allow non-natural reactions in biological settings. Grubbs-Hoveyda type ruthenium catalysts with an N-heterocyclic carbene (NHC) as ancillary ligand, known to be active in olefin metathesis, have recently been incorporated in various proteins. An overview of these artificial metalloproteins and their potential application in olefin metathesis is given.

Formation of α-[KSiH3] by hydrogenolysis of potassium triphenylsilyl.

Hydrogenation of easily accessible potassium triphenylsilyl [K(Me6TREN)SiPh3] gave the hydrogen storage material α-[KSiH3] in high yields by an unusual hydrogenolytic cleavage of silicon-phenyl bonds.

Impact of single-port cholecystectomy on postoperative pain.

BACKGROUND: This study compared postoperative pain following four-port laparoscopic cholecystectomy (LC) and single-port cholecystectomy (SPC). METHOD: This prospective, quasi-randomized, single-centre trial focusing on postoperative pain included 49 patients undergoing elective surgery with either a conventional LC, or SPC using a surgical glove port. Postoperative pain was evaluated using a visual analogue scale (VAS) and postoperative analgesic use as primary outcome measures. Total duration of operation, length of hospital stay, blood test results on the day after surgery and total port cost were secondary outcome measures. RESULTS: Twenty-five LCs and 24 SPCs were undertaken. The VAS score on day 1 after surgery was significantly less in the SPC group than in the LC group: median (range) 24 (12-38) versus 45 (33-57) mm (P = 0·002). Significantly fewer patients in the SPC group required analgesia (9 of 24 versus 19 of 25 in the LC group; P = 0·007). There were no significant differences in total duration of operation, length of hospital stay, and blood test results on the day after surgery. CONCLUSION: Single-port surgery using a surgical glove port reduces postoperative pain compared with conventional LC.

Safe anastomosis in laparoscopic low anterior resection for rectal cancer.

INTRODUCTION: In laparoscopic rectal surgery, there are some limitations on a surgeon's ability to maneuver, especially in transection of the lower rectum. To achieve minimally invasive surgery, safe anastomosis, including proper rectal transaction, is necessary. METHODS: To overcome the difficulty in lower rectal resection, we followed a series of steps. First, we completely mobilized the rectum to the pelvic bottom, just above the anal canal, making the lower rectum mobile and allowing for an easy rectal transection. To secure the transaction, the mesorectum around the transection must be properly divided. We recommend placing the lower right quadrant port as caudal as possible to properly staple the rectum. We found a 60 mm compression-type stapler most suitable for rectal transection. To wash and flatten the rectum, a detachable intestinal clip is quite useful because of its flexibility. Finally, in addition to conventional abdominal drains around the anastomotic site, we employed transanal tube to actively decompress rectal pressure inside the anastomotic site. RESULTS: Between August 2009 and July 2010, 101 patients underwent laparoscopic low anterior resection using this technique. Most patients, 98.0% (99/101), underwent lower rectum transection using a single-fire cartridge. The anastomotic leakage rate was only 1.0% (1/101) in total and 1.3% (1/78), when not including patients with diverting stoma. CONCLUSION: We have to follow up with more patients to conclude whether our technique is effective in the long term. However, this step-by-step technique could lead to safe anastomosis in laparoscopic low anterior resection for rectal cancer.

The Endoscopic Surgical Skill Qualification System for gastric surgery in Japan.

INTRODUCTION: Laparoscopic surgery has been increasing in popularity in recent years. In 2004, the Japan Society for Endoscopic Surgery developed its Endoscopic Surgical Skill Qualification System (ESSQS) to assess surgeons. METHODS: To earn the ESSQS accreditation, applicants must submit an unedited operative video in which they perform either a distal gastrectomy or pylorus-preserving gastrectomy with lymph node dissection for gastric cancer. The videos are assessed by two separate judges based on detailed criteria for common and procedure-specific technical-grade slips. Common criteria from all fields of gastrointestinal and general surgery are used to evaluate the basic laparoscopic surgical skills and autonomy of the operator. The target organ determines the procedure-specific criteria are set to assess whether or not adequate oncological clearance has been achieved. RESULTS: Between 2004 and 2009, 154 (44.6%) out of 345 applicant surgeons assessed under the ESSQS for gastric surgery have been accredited. Interrater agreement was acceptable and ranged between 0.21 and 0.59. CONCLUSION: The ESSQS system may facilitate improvement in surgical technique and the standardization of laparoscopic surgery in Japan.

Cell wall fraction of Enterococcus hirae ameliorates TNF-alpha-induced barrier impairment in the human epithelial tight junction.

AIMS: The evaluation of the effects of Enterococcus hirae, an intestinal bacterium in the adjacent mucosa (mucosal bacterium), on tumour necrosis factor-alpha (TNF-alpha)-induced barrier impairment in human epithelial Caco-2 cells. METHODS AND RESULTS: The filter-grown Caco-2 monolayers were used as an intestinal epithelial model system. In Caco-2 cells, heat-killed E. hirae ATCC 9790(T) suppressed the TNF-alpha-induced barrier impairment and increase in interleukin-8 (IL-8) secretion, but lipase- and mutanolysin-treated E. hirae ATCC 9790(T) did not have these effects. It was demonstrated that lipoteichoic acid (LTA) from E. hirae ATCC 9790(T) is responsible for Caco-2 cells' recovery from TNF-alpha-induced impairments. In addition, Caco-2 cells had the same response to Toll-like receptor 2 (TLR2) ligand, Pam(3)Cys-Ser-(Lys)(4) as they did to LTA. Increased expression of zonula occludens-1 was observed by the addition of E. hirae ATCC 9790(T) to TNF-alpha-treated Caco-2 cells, and decreased expression of myosin light chain kinase was observed by the addition of LTA and Pam(3)Cys-Ser-(Lys)(4); this, in turn, led to barrier enforcement. CONCLUSIONS: Enterococcus hirae ATCC 9790(T) cell wall fractions, such as LTA, protect against intestinal impairment by regulation of epithelial tight junction via TLR2 signalling. SIGNIFICANCE AND IMPACT OF THE STUDY: Enterococcus hirae could be useful in the treatment of inflammatory bowel disease, as well as other intestinal disorders.

Virtual CT colectomy by three-dimensional imaging using multidetector-row CT for laparoscopic colorectal surgery.

Laparoscopic colorectal surgery has been attracting attention for its capacity to improve the quality of life (QOL) of patients. However, there are disadvantages to this approach, namely, it is difficult to obtain an image of the entire view of the operative field, and organs and lesions cannot be manipulated directly by the surgeon during surgery. For this reason, it takes a relatively large amount of time to ligate vessel, which can vary between patients. Furthermore, vessels and organs can be damaged during lymph nodes dissection under laparoscopic guidance, leading to heavy bleeding that prevents the surgeon from having access to a good view of the operative field. Then, to assess preoperatively the vascular anatomy, we carried out multiphase, contrast-enhanced examinations using multidetector-row CT (MDCT) on patients with colorectal cancer, and prepared the fused image of 3D images of arteries, veins, the colorectum, organs, and tumor. We called the utilization of 3D imaging virtual CT colectomy, which contributed to rapid and safe manipulation of the origins of the arteries and the veins, as well as lymph nodes dissection, without incurring injury to the involved arteries and veins.

Correlations of hemoglobin index (IHb) of gastric mucosa with Helicobacter pylori (H. pylori) infection and inflammation of gastric mucosa.

BACKGROUND: Helicobacter pylori (H. pylori) infection causes various gastric diseases, among them H. pylori-associated gastritis characterized by diffuse redness of the gastric mucosa. The haemoglobin index (IHb) of the fundic mucosa is an objective parameter of the extent of mucosal redness, but it is unclear whether or not IHb can be used as a diagnostic marker for H. pylori infection. The purpose of this investigation was to evaluate the correlations between IHb of the fundic mucosa and H. pylori infection, inflammatory cell infiltration, and inflammatory mediator production. METHODS: IHb of the fundic mucosa was measured in 108 patients with various gastric diseases (group 1), and values were compared between H. pylori-positive and H. pylori-negative patients. Fifteen patients with H. pylori infection from group 1 underwent H. pylori eradication therapy and IHb was measured before and after treatment. Both IHb and inflammatory cell infiltration were assessed in 61 patients (group 2). In 31 patients from group 2, the expression of interleukin (IL)-8 and inducible nitric oxide synthase (iNOS) messenger RNA (mRNA) was assayed in gastric biopsy specimens by the reverse transcription-polymerase chain reaction (RT-PCR). RESULTS: IHb levels were significantly higher in H. pylori-positive patients than in H. pylori-negative patients (P < 0.001). IHb was decreased at one month after the eradication of H. pylori (P < 0.001). IHb was higher in patients with infiltration by both mononuclear cells and neutrophils (P < 0.001). There was a significant correlation between the IHb level and the expression of IL-8 mRNA (P < 0.001), as well as between IHb and iNOS mRNA expression (P < 0.05). CONCLUSIONS: There were significant correlations between IHb of the gastric mucosa and H. pylori infection, inflammatory cell infiltration, and IL-8/iNOS mRNA expression, suggesting that IHb is a reliable marker of H. pylori infection for use during follow-up endoscopy after H. pylori eradication therapy.

Laparoscopic approach for early gastric cancer within a paraesophageal hiatal hernia.

We present a case of early gastric cancer located in gastric volvulus associated with paraesophageal hiatal hernia. Two lesions of EGC were diagnosed in the distal third of the stomach, most of which had herniated into the left chest through a large hiatal defect in an organoaxial fashion. Routinely, laparoscopic-assisted distal gastrectomy (LADG) is our preferred approach for EGC, and the presence of hiatal hernia in this case did not alter our approach. Laparoscopic repair of hiatal hernia was performed successfully followed by LADG. A review of the literature supports a minimally invasive approach for both procedures and shows it to be safe, effective, and technically feasible. Further, LADG is shown to be oncologically adequate in terms of tumor margins and lymph node dissection, but its relevance to long-term disease-free survival still needs to be studied in well-designed prospective trials.

Formant interaction as a cue to vowel perception: a case report.

Accumulating evidence indicates that cerebral processing of consonants and vowels is separable. It has been shown that disordered temporal acuity leads to disturbed consonant perception in cases with pure word deafness. In contrast, there has been no clear explanation of how vowel perception is impaired. We examined a patient with auditory agnosia, who showed a differential ability to identify the five Japanese vowels after bilateral cerebral lesions. He correctly identified the vowel [a] in more than 70% of auditory presentations, whereas he identified [i] in only about 30% of presentations. The difference between the first and second formant frequencies "F2-F1" and an artificially defined value "F1-(F2-F1)" for each vowel correlated significantly with the percentage of correct identifications. These findings support the hypothesis that vowel perception is based on formant interactions.

Recombinant monoclonal thyrotropin-stimulation blocking antibody (TSBAb) established from peripheral lymphocytes of a hypothyroid patient with primary myxedema.

Anti-TSH receptor antibodies (TRAbs) have been known to be involved in Graves' disease and primary hypothyroidism. We previously isolated and reconstituted immunoglobulin (Ig) genes of Epstein-Barr virus-transformed B cell clones producing monoclonal TRAbs obtained from Graves' patients. In the present study, we performed a similar experiment using a B cell clone, 32A-5, derived from a patient with primary hypothyroidism. The variable region genes of Ig heavy (H) and light (L) chains were isolated and sequenced from the 32A-5 clone. A significant number of somatic mutations were found in variable regions of H and L chain gene segments. Each pair of H and L chain cDNAs was ligated into an expression vector for IgG1 production and stably introduced into myeloma cells. The transfectants were injected ip into BALB/c mice to yield ample volume of the antibody for following applications. Interactions of recombinant 32A-5 with Graves' sera with varying thyroid-stimulating antibody (TSAb) activities were studied. The recombinant antibody tended to suppress TSAb activities in 10 of 15 Graves' sera, in which four were significantly inhibited. In summary, this is the first study to analyze human monoclonal TSH-stimulation blocking antibodies (TSBAb) at the molecular level. Use of human recombinant monoclonal TSBAb may be an analytical tool for molecular-basis etiology and an alternative therapeutic path for Graves' disease.

Brain activation during the fist-edge-palm test: a functional MRI study.

The purpose of our study is to clarify, using functional MRI, brain regions activated during the fist-edge-palm task (FEP) compared to relatively simple hand motor tasks using either the right or the left hand in right-handed normal volunteers. The FEP was introduced to detect a disorder of voluntary movement, and it is believed to be closely related to contralateral frontal lobe damage. However, this assumption still remains controversial. Ten subjects participated in this study. Hand motor tasks were as follows: (1) the FEP, in which the subjects were requested to place their hand in three different positions sequentially: a fist resting horizontally, a palm resting vertically, and a palm resting horizontally; (2) a fist-palm task (FP), in which the subjects were asked to clench and unclench their fist alternately; and (3) a control task requiring the subjects to knock lightly with their clenched fist. The contralateral sensomotor and premotor areas were activated in the FP with the right hand and the contralateral sensorimotor, premotor, and supplementary motor areas (SMA) were activated in the FP with the left hand. In the FEP with either hand, bilateral premotor and left parietal areas and ipsilateral cerebellum were also activated as well as contralateral sensorimotor area and SMA. Our results suggest that successful performance of the FEP requires the participation of more brain areas than FP, which may explain why some patients without frontal lobe damage failed to perform the FEP.

[A patient with recurrent breast cancer whose liver metastasis regressed following combined use of weekly docetaxel and MPA.5'-DFUR].

A 28-year-old woman who was 10 months pregnant was diagnosed with left breast cancer. She received preoperative chemotherapy and underwent mastectomy after parturition. Endocrine therapy and adjuvant CMF and CAF was administered, but a bone metastasis appeared 2 years later and a liver metastasis 3 years later. Weekly docetaxel and MPA plus 5'-DFUR combination therapy were successively and simultaneously administered. The liver tumor regressed, and the survival time was prolonged by 1 year and 6 months. This case suggests that the combined use of both therapies was safe for the patient in serious bad condition and had a strong antitumor effect.