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The NBS bromination of 1,4-dimethoxy-2,3-dimethylbenzene has been examined under a variety of conditions in both 1,1,1-trichloroethane and benzotrifluoride. Four different bromination products have been isolated including the previously unknown 1-bromo-4-bromomethyl-2,5-dimethoxy-3-methylbenzene whose single crystal X-ray structure is presented. The synthetically useful 2,3-bis(bromomethyl)-1,4-dimethoxybenzene is readily prepared using either solvent and it has been converted into new sulfur-containing quinone derivatives Postprint

The Engineering and Physical Sciences Research Council (EPSRC) is acknowledged for the funding of FG (EP/M029077/1) and RM (EP/506631/1). FG also acknowledges the European Union for funding the SURMOF project under which part of this work was undertaken (contract number NMP4-CT-2006-032109). The structure and surface chemistry of ultrathin metallic films of one metal on another are strongly influenced by factors such as lattice mismatch and the formation of near-surface alloys. New morphologies may result in modified chemical properties which in turn open up different routes for molecular adsorption, desorption and surface functionalization, with important consequences in several fields of application. The Cu/Au(111) system has received the attention of many studies, only a few however have been performed in ultra-high vacuum (UHV), using surface sensitive techniques. In this contribution, the room temperature deposition of copper onto the (22×√3)-Au(111) surface, from submonolayer to thick film, is investigated using scanning tunnelling microscopy (STM). The onset of copper adsorption is seen to occur preferentially at alternate herringbone elbows, with a preference for hcp sites. With increasing coverage, copper-rich islands exhibit a reconstructed surface reminiscent of the clean Au(111) herringbone reconstruction. Disordered, pseudo-ordered and ordered surface layers are observed upon annealing. Models for the initial adsorption/incorporation mechanism, formation of adlayers and evolution with increasing coverage and annealing are qualitatively discussed. Further, the reactivity of copper-doped Au(111) systems is considered towards the adsorption of organic molecules of interest in nanotechnology and their catalytic applications. Publisher PDF

Background Laparoscopic donor nephrectomy may convert short main arteries into multiple arteries, increasing the technical challenge of implantation. We evaluated our experience to identify factors predictive of multiple arteries after laparoscopic nephrectomy. Methods All laparoscopic nephrectomies from the start of our program in November 2002 until June 2013 were studied, and preoperative imaging reviewed for donor artery length and multiplicity together with operative findings. Results A total of 287 consecutive laparoscopic live donor nephrectomies (64 right and 223 left nephrectomies) were studied. Renal artery length was measured from preoperative donor magnetic resonance or computed tomography angiogram and nephrectomy performed using a laparoscopic stapling device. Nine left kidneys with a single artery (6, 7, 9, 10, 11, 12, 13, 14, and 16 mm in length) and five right kidneys with a single artery (5, 13, 15, 20, and 26 mm) on imaging resulted in multiple renal arteries at implantation. Complex renal vein anatomy was associated with multiple arteries following retrieval. Conclusion A main renal artery length of more than 16 mm on the left and 26 mm on the right is unlikely to result in multiple arteries to implant. The possibility of multiple arteries should be borne in mind when the donor renal artery is short.

We investigated the relationship between preoperative comorbidity and postoperative survival after intestinal transplantation. Each patient received a score for preoperative comorbidity. Each comorbidity was given a score based on the degree it impaired function (score range 0-3). A total score was derived from the summation of individual comorbidity scores. Patients (72 adults (M : F, 33 : 39)) received an isolated intestinal graft (27) or a cluster graft (45). Mean (standard deviation) survival was 1501 (1444) days. The Kaplan-Meier analysis revealed a significant inverse association between survival and comorbidity score (logrank test for trend, P < 0.0001). Patients grouped into comorbidity scores of 0 and 1, 2 and 3, 4 and 5, 6, and above had hazard ratios (95% confidence intervals) for death (compared to group 0 + 1), which increased with comorbidity scores: 1.945 (0.7622-5.816), 5.075 (3.314-36.17), and 13.77 (463.3-120100), respectively, (P < 0.0001). Receiver-operator curves at 1, 3, 5, and 10 years postoperative had "C" statistics of 0.88, 0.85, 0.88, and 0.92, respectively. When evaluating patients for transplantation, the degree of comorbidity should be considered as a major factor influencing postoperative survival.

Objectives The aims of this study were to (i) identify independent predictors of survival after pancreaticoduodenectomy for ampullary cancer and (ii) develop a prognostic model of survival. Methods Data were analyzed retrospectively on 110 consecutive patients who underwent pancreaticoduodenectomy between 2002 and 2013. Subjects were categorized into 3 nodal subgroups as per the recently proposed nodal subclassification: N0 (node negative), N1 (1–2 metastatic nodes), or N2 (≥3 metastatic nodes). Clinicopathological features and overall survival were compared by Kaplan-Meier and Cox regression analyses. Results The overall 1-, 3-, and 5-year survival rates were 79.8%, 42.2%, and 34.9%, respectively. The overall 1-, 3-, and 5-year survival rates for the N0 group were 85.2%, 71.9%, and 67.4%, respectively. The 1-, 3-, 5-year survival rates for the N1 and N2 subgroups were 81.5%, 49.4%, and 49.4% and 75%, 19.2%, and 6.4%, respectively (log rank, P < 0.0001). After performing a multivariate Cox regression analysis, vascular invasion and lymph node ratio were the only independent predictors of survival. Hence, a prediction model of survival was constructed based on those 2 variables. Conclusions Using data from a carefully selected cohort of patients, we created a pilot prognostic model of postresectional survival. The proposed model may help clinicians to guide treatments in the adjuvant setting.

Financial support by the Friedrich Ebert-Stiftung to M.K. is gratefully acknowledged. The work of B.Y. at the Georgia Institute of Technology was supported by Grant FA9550-14-1-0005 from the U.S. Air Force Office of Scientific Research, and the work of U.L. was supported in part by a Grant FG05-86ER45234 from the Office of Basic Energy Sciences of the U.S. Department of Energy.R.S. and N.V.R. acknowledge financial support from the Scottish Funding Council through EaStCHEM and SRDG Grant HR07003. R.S. and H.F. acknowledge EPSRC for the use of the ARCHER U.K. National Supercomputing service, and for the funding of PhD studentships (JAGT − EP/M506631/1, and MJT − EP/K503162/1). Diverse technologies, from catalyst coking to graphene synthesis, entail hydrocarbon dehydrogenation and condensation reactions on metals, and assembly into carbon overlayers. Imperative to gaining control over these processes, through thermal steering of the formation ofpolyaryl intermediates and the controlled prevention of coking, is the exploration and elucidation of the detailed reaction scheme that starts with adsorbed hydrocarbons and culminates with the formation of extended graphene. Here we use scanning tunneling microscopy, high-resolution electron energy loss and thermal desorption spectroscopies, in combination with theoretical simulations to uncover the hierarchy of pathways and intermediates underlying the catalyzed evolution of ethene adsorbed on Rh(111) to form graphene. These investigations allow formulation of a reaction scheme whereby, upon heating, adsorbed ethene evolves via coupling reactions to form segmented one-dimensional polyaromatic hydrocarbons (1D-PAH). Further heating leads to dimensionality crossover (1D→2D) and dynamical restructuring processes at the PAH chain ends, with subsequent activated detachment of size-selective carbon clusters. Rate-limiting diffusional coalescence of these dynamically self-evolved precursors culminates (≤1000 K) in condensation into graphene of high structural perfection. Publisher PDF

The first intestinal transplantation in the United Kingdom was performed in Cambridge in 1991. Thirty-eight intestinal transplantations have since been performed in 35 patients. All deaths in the first postoperative month related to hemorrhage, in 2 cases to severe portal hypertension (SPH) and poor venous access in 2. We have modified our practice to reduce the bleeding risk with SPH. Loss of venous access can be avoided by timely referral. Rejection was implicated in 3/14 deaths all dying of sepsis. Cytomegalovirus disease resulted in 2 deaths; we try to avoid CMV-positive donors giving to CMV-negative recipients. Three deaths were related to psychiatric illness, which led to loss of graft in 2 others. Three patients were retransplanted (2 rejections and 1 infarction) and all remain alive. Most patients (10/13) experienced a fall in body weight in the first postoperative year after SB/MV transplantation. Body weight fell by as much as 25%. As transplantation resulted in a net gain in small bowel in most cases, the postoperative loss of native body weight may be underestimated. Interestingly this was not associated with a significant fall in midarm circumference or handgrip strength. Long-term nutrition can be maintained with oral intake in the majority of patients post-SBT. There is improvement in handgrip strength post-transplant. Transplantation does not significantly alter weight, albumin, or other common anthropometric markers. Despite these problems, our 5-year survival results remain relatively good at 73% in the cohort from 1991, 79% from 2003, and 80% from 2008. We consider that deployment of strategies learned from our experiences has improved outcomes.

Background and Objectives Actual long-term survival of patients with colorectal liver metastases staged by PET CT has not been reported. Objectives were to investigate whether PET CT staging results in actual improved long-term survival, to examine outcome in patients with ‘equivocal’ PET CT scans, and those excluded from hepatectomy by PET CT. Methods A retrospective analysis of patients undergoing hepatectomy for colorectal liver metastases between March 1998 and September 2008. Results Overall 5- and 10-year survival was 44.8% and 23.9%. PET CT staging resulted in management changes in 23% of patients. PET CT staged patients showed significantly better survival than those staged by CT alone at 3 years (79.8% vs. 54.1%) and at 5 years (54.1% vs. 37.3%) with median survivals of 6.4 years versus 3.9 years (log rank P = 0.018). Patients with equivocal PET CT scans showed worse median survival than those with favourable PET CT (log rank P = 0.002), but may include a subpopulation whose prognosis trends towards a more favourable outcome than those excluded from liver resection by PET CT, whose median survival remains limited to 21 months. Conclusions Staging of patients with colorectal liver metastases by PET CT is associated with significantly improved actual long-term survival, and provides valuable prognostic information which guides surgical and oncological treatments. J. Surg. Oncol. 2014 110:313–319. © 2014 Wiley Periodicals, Inc.

Benzotriazole (BTAH) has been used as a copper corrosion inhibitor since the 1950s. However, the molecular level detail of how adsorption and surface passivation occur remains a matter of debate. BTAH adsorption on a Cu(111) single crystal has been investigated from medium coverage to multilayer using scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), high resolution electron energy loss (HREEL) spectroscopy and supporting density functional theory (DFT) calculations. Both physisorbed and chemisorbed phases are observed. One extended and highly ordered self-assembled metal−organic phase is seen at saturation coverage and above. A metastable phase is also observed. Complete desorption occurs at ca. 600 K. Those structures are critically discussed in the light of some of the various adsorption models reported in the literature and an alternative adsorption model is proposed. These results allow a further understanding of the interaction between benzotriazole and copper and, in tur...

A dihydro-TTF derivative with four acetyl-protected thiol ligands was synthesised and adsorbed on Au(111) under UHV conditions. Scanning Tunnelling Microscopy (STM) and Infrared (IR) spectroscopy show that self-organised structures are formed following annealing to 333 K, with each pair of bidentate thiolate ligands bonding to a single gold adatom in a S-Auad-S complex. Due to the lack of a direct orbital overlap between the dihydro-TTF moieties and the surface, relatively little charge transfer between TAT-TTF and the gold surface occurs.

INTRODUCTIONPrimary closure of the abdominal wall following intestinal transplantation or multivisceral transplantation could become a challenging problem in a significant number of patients.PRESENTATION OF CASEA 38-year-old woman with familial adenomatous polyposis (FAP) underwent a multi-visceral transplantation for short gut syndrome. She subsequently developed acute graft rejection that proved resistant to conventional treatment. She was relisted and underwent re-transplantation along with kidney transplantation. Abdominal wall closure could not be achieved because of the large size of the graft and bowel oedema. The wound was initially managed with laparostomy followed by insertion of the delayed dynamic abdominal closure (DDAC) device (Abdominal Retraction Anchor – ABRA® system). Continuous dynamic traction to the wound edges resulted in gradual approximation and complete closure of the abdominal wound was achieved within 3 weeks.DISCUSSIONSuccessful abdominal closure after multivisceral transplantation or isolated intestinal transplantation often requires biological mesh, vascularised flaps or abdominal wall transplantation. DDAC eliminated the need for a prosthetic mesh or skin graft and provided an excellent cosmetic result. Adjustment of the dynamic traction at the bedside minimised the need for multiple returns to the operating theatre. It resulted in a well-healed linear scar without a hernia.CONCLUSIONDynamic traction allows delayed closure of laparotomy resulting in strong and cosmetically sound wound healing with native tissue.

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We acknowledge the support of the Wellcome Trust for a grant to RL, CPP and NVR to support some of this work. The properties of commercially prepared heparin as an anticoagulant and antithrombotic agent in medicine are better understood than is the physiological role of heparin in its native form, where it is uniquely found in the secretory granules of mast cells. In the present study we have isolated and characterised the glycosaminoglycans (GAGs) released from degranulating rat peritoneal mast cells. Analysis of the GAGs by NMR spectroscopy showed the presence of both heparin and the galactosaminoglycan dermatan sulphate; heparinase digestion profiles and measurements of anticoagulant activity were consistent with this finding. The rat peritoneal mast cell GAGs significantly inhibited accumulation of leukocytes in the rat peritoneal cavity in response to IL-1β (p

Background In 1996 two transplantation centres in the UK were commissioned by the National Specialist Commissioning Advisory Group for England and Wales to assess small intestinal transplantation in adults. The joint experience of the two centres is presented. Methods Patients with irreversible small intestinal failure and complications of parenteral nutrition, and those with abdominal disease requiring extensive visceral resection, were assessed as candidates and where appropriate listed for surgery. Results Thirty-six patients were assessed for small intestinal transplantation and, of these, 14 underwent surgery. Twelve patients survived the transplantation procedure. Of these, seven patients were alive at 1 year, five at 3 years and three at 5 years. Three patients remain alive. Patient and graft survival improved with experience; the 1-year survival rate improved in the last 4 years of this experience from 43 to 57 per cent, and the 3-year survival rate from 29 to 43 per cent. Conclusion Small intestinal transplantation is associated with a high mortality rate but may benefit carefully selected patients in whom conservative management is likely to carry a greater mortality rate.

BACKGROUND: Campath 1H is a depleting, humanized anti-CD52 monoclonal antibody that has now been used in 31 renal allograft recipients. The results have been very encouraging and are presented herein. METHODS: Campath 1H was administered, intravenously, in a dose of 20 mg, on day 0 and day 1 after renal transplant. Low-dose cyclosporine (Neoral) was then initiated at 72 hr after transplant. These patients were maintained on low-dose monotherapy with cyclosporine. RESULTS: At present, the mean follow-up is 21 months (range: 15-28 months). All but one patient are alive and 29 have intact functioning grafts. There have been six separate episodes of steroid-responsive rejection. One patient has had a recurrence of her original disease. Two patients have suffered from opportunistic infections, which responded to therapy. One patient has died secondary to ischemic cardiac failure. CONCLUSIONS: Campath 1H has resulted in acceptable outcomes in this group of renal allograft recipients. This novel therapy is of equal efficacy compared to conventional triple therapy, but allows the patient to be steroid-free and to be maintained on very-low-dose immunosuppressive monotherapy.

Post-operative pancreatic fistula (POPF) is the major source of morbidity following pancreaticoduodenectomy. A predictive indicator would be highly advantageous. One potential marker is drain amylase concentration (DAC). However, its predictive value has not been fully established.405 patients undergoing pancreaticoduodenectomy at our centre over a 10 year period were reviewed to determine the value of DAC as a predictive indicator for the development of POPF.POPF developed in 58 patients (14%). These patients suffered greater morbidity. Overall 30-day mortality was 1.5%. Male gender (OR: 5.1; p = 0.0082) and age 70 (OR 2; p = 0.0372) were independent risk factors for POPF, whilst Type 2 diabetes (OR: 0.2321; p = 0.0090) and pancreatic ductal-adenocarcinoma (OR: 0.3721; p = 0.0039) decreased POPF risk. The DACs post-operatively were significantly higher in those developing POPF, but with significant overlap. ROC curves revealed optimal threshold values for differentiating POPF and non-POPF patients. A DAC°°1400 U/ml on day 1 and768 U/ml on day 2, although having a poor positive predictive value (32-44%), had a very strong negative predictive value (97-99%).Our data suggest that post-operative DAC below the determined optimal threshold values on day 1 and 2 following pancreaticoduodenectomy carries high negative predictive value for POPF development and identifies patients in whom early drain removal, and enhanced recovery may be considered, with simultaneous assessment of operative and clinical factors.

International audience; BACKGROUND:We investigated whether sirolimus-based immunosuppression improves outcomes in liver transplantation (LTx) candidates with hepatocellular carcinoma (HCC).METHODS:In a prospective-randomized open-label international trial, 525 LTx recipients with HCC initially receiving mammalian target of rapamycin inhibitor-free immunosuppression were randomized 4 to 6 weeks after transplantation into a group on mammalian target of rapamycin inhibitor-free immunosuppression (group A: 264 patients) or a group incorporating sirolimus (group B: 261). The primary endpoint was recurrence-free survival (RFS); intention-to-treat (ITT) analysis was conducted after 8 years. Overall survival (OS) was a secondary endpoint.RESULTS:Recurrence-free survival was 64.5% in group A and 70.2% in group B at study end, this difference was not significant (P = 0.28; hazard ratio [HR], 0.84; 95% confidence interval [95% CI], 0.62; 1.15). In a planned analysis of RFS rates at yearly intervals, group B showed better outcomes 3 years after transplantation (HR, 0.7; 95% CI, 0.48-1.00). Similarly, OS (P = 0.21; HR, 0.81; 95% CI, 0.58-1.13) was not statistically better in group B at study end, but yearly analyses showed improvement out to 5 years (HR, 0.7; 95% CI, 0.49-1.00). Interestingly, subgroup (Milan Criteria-based) analyses revealed that low-risk, rather than high-risk, patients benefited most from sirolimus; furthermore, younger recipients (age ≤60) also benefited, as well sirolimus monotherapy patients. Serious adverse event numbers were alike in groups A (860) and B (874).CONCLUSIONS:Sirolimus in LTx recipients with HCC does not improve long-term RFS beyond 5 years. However, a RFS and OS benefit is evident in the first 3 to 5 years, especially in low-risk patients. This trial provides the first high-level evidence base for selecting immunosuppression in LTx recipients with HCC.TRIAL REGISTRATION:ClinicalTrials.gov NCT00355862.

Background Multivisceral transplantation (transplantation of the stomach, intestine, liver, and pancreas) is usually undertaken as a semi-elective procedure after thorough assessment in patients who have intestinal failure with cirrhosis, cirrhosis with portomesenteric venous thrombosis, or tumors such as desmoids involving the liver and mesentery. Study Design Data were collected prospectively from the time of referral and held in a central database. We used it to report the first cases of urgent multivisceral transplantation (MVT) in patients with widespread splanchnic ischemia (occlusion of the celiac axis and superior mesenteric artery) resulting in small bowel infarction and hepatic failure. Results Three women (ages 33, 48, and 50 years) were referred to our center with superior mesenteric artery and celiac axis occlusion. All other modes of treatment had been considered and/or attempted. After transfer to our institution, all patients were assessed, urgently listed, and underwent transplantation in 10, 7, and 5 days. Two patients are still alive after 2 years and 1 died at 8 months from multiorgan failure due to infections and graft vs host disease. Conclusions Treatment options for patients presenting with widespread splanchnic ischemia with hepatic and intestinal failure/infarction were previously limited to salvage surgery and attempted revascularization. In situations in which these failed, the only previous option would have been palliation. In selected cases, we propose that urgent multivisceral transplantation should be considered as a life-saving treatment. This represents a previously unreported indication for MVT.

Background Laparoscopic adrenalectomy (LA) is the gold standard for benign adrenal resection, and has been performed at our centre since 2000. We present a retrospective audit of our ten-year experience, and discuss the learning curve. Methods Creating a retrospective database, clinical and outcome data were collected for all resections performed over a ten-year period (2000–2010). Patients were chronologically divided into an ‘early' (first 40 cases) and ‘late' (subsequent cases) group to provide an insight into the learning curve. Results Over this period, 134 laparoscopic resections were performed, predominantly for benign adenomas (80.3%), with 48% of patients having primary hyperaldosteronism. There was almost equal sex distribution and mean age was 50.2 years, with a median BMI of 28.2. The mean operating time for left and right procedures were 127 and 124 min respectively, with 56.7% of resections being left sided. Our rate of conversion to open was 3.9%. Median length of stay was 4 days post-operatively. There was no mortality and 8.7% patients experienced a surgical complication. Analysis of the grouped data demonstrated a statistically significant reduction in open conversion rate ( p = 0.017) and operative time ( p = 0.011) in the ‘late' group. Among the two groups there was no statistically significant difference in the length of stay and surgical complication rate. All results were comparable to published series in the literature. Conclusion LA has proven to be a safe procedure with a low complication rate at our centre. Our data provide evidence that operative time and conversion rate improves with experience.

The use of integration of copper interconnects in semiconductor devices has greatly advanced the development of integrated circuits and has enabled ever higher device densities. Unfortunately the oxides of copper are poorly suited to semiconductor manufacture. As Cu (I) and Cu (II) oxides are not self-limiting they can pose serious issues from a cleaning and queue time management perspective. In both post-etch and post-CMP cleaning applications it is critical that both types of Cu oxide are removed without damage to either Cu or the dielectric. With the most advanced sub 32nm nodes simply removing the oxides is not sufficient; their re-growth must also be prevented using surface passivation.

Syntheses and full characterisation data (including single crystal diffraction) of three 1,2-diphosphonium dicationic species with the naphthalene-1,8-diyl (Nap) backbone are reported. The oxidation of Nap[P(NMe(2))(2)](2) with P(2)I(4) to its 1,2-dication was achieved. meso- and rac-forms of "all carbon" 1,2-diphosphonium dications were obtained in good yields and purity by double alkylation of the parent diphosphine (1,2-diphenyl-1,2-diphosphaacenaphthene) with methyl triflate or trimethyloxonium tetrafluoroborate. Each methylating reagent produces one of the rac- or meso-forms of the dication diastereospecifically. Structural parameters of the new dications are discussed with respect to other phosphorus 1,2-dications. DFT (B3LYP) computations revealed the significant role of the naphthalene backbone in stabilisation of the dicationic motif and helped to assess the energy cost of the steric clash of a variety of groups attached to the peri-positions of naphthalene. The synthesis and single crystal X-ray data of the extremely crowded Nap[P(Se)(OiPr)(2)](2) are discussed, and are contrasted with the unsuccessful synthesis of Nap(PtBu(2))(2) from NapLi(2) and ClPtBu(2).

Background Many patients referred for intestinal transplantation have a history of thrombosis. We undertook an analysis of transplanted patients to describe the history and frequency of thrombosis, clinical course, and management strategies used. Results Twenty-five patients underwent transplantation of intestine containing blocks between 2007 and 2012; 20 of 25 are still alive. Five of 25 patients were transplanted with history of portomesenteric thrombosis, 6 of 25 had experienced loss of venous access due to thrombosis, and 6 of 25 had history of mesenteric ischemia. Pretransplantation, 16 of 25 patients were anticoagulated. Thrombophilia screens identified 3 of 16 patients who were JAK2 positive, 1 of 25 who had antithrombin deficiency, and 1 of 25 who had a factor V Leiden heterozygote. Post-transplantation, of all 16 patients who were anticoagulated pretransplantation and continued postoperatively, 1 of 16 infarcted their small bowel graft and 4 of 16 developed a further venous thrombosis despite anticoagulation. Of the 9 without a previous history of thrombosis, 1 had a pulmonary embolus more than a decade after transplantation and another had an upper limb deep vein thrombosis associated with a line. Both were then anticoagulated. Seven of 25 are not anticoagulated, although they are administered antiplatelet prophylaxis. Postoperative bleeding complications of anticoagulation occurred in 3 patients. After a subarachnoid hemorrhage in 1 of those 3 patients, anticoagulation was stopped. The other 2 patients bled during ileal biopsy, and both remain on low molecular weight heparin treatment. Conclusion Those with identifiable thrombophilic tendency and a history of venous or arterial thrombosis are considered to be at high risk for recurrent thrombosis. Those without such a history could be considered low risk. Our practice is to anticoagulate all high-risk individuals before and after transplantation and offer antiplatelet prophylaxis to low-risk patients as the risk of anticoagulation probably outweighs the risk of thrombosis for them. Early input from hematologists is vital in the management of high-risk patients, particularly those who thrombose when anticoagulated.