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71.
72.
A case of multifocal malignant peripheral neuroectodermal tumor (PNET) arising from a plexiform neurofibroma in a 4-month-old Chinese boy with neurofibromatosis type 1 (NF-1) is described. Cytogenetic culture demonstrated hypotriploid karyotype with an abnormal clone characterized by 59–60, XY, +2, +3, +6, +8, +8, +12, +i(13)(q10), +der(14)t(1;14)(q21;q32), +16, +19, +20, +mar[cp3] with no apparent abnormality of chromosome 17. The child was treated with combination chemotherapy comprising ifosphamide, vincristine and doxorubicin. Despite initial partial response the child finally died of tumor progression and pulmonary metastases 8 months after diagnosis. We believe this is the first reported case of PNET in a child with NF-1 and may support an association between these two disorders of neural crest origin. © 1996 Wiley-Liss, Inc.  相似文献   
73.
Gold surface-bound hyperbranched polyethyleneimine (PEI) films decorated with palladium nanoparticles have been used as efficient catalysts for a series of Suzuki reactions. This thin film-format demonstrated good catalytic efficiency (TON up to 3.4 × 103) and stability. Incorporation into a quartz crystal microbalance (QCM) instrument illustrated the potential for using this approach in lab-on-a-chip-based synthesis applications.

Gold surface-bound hyperbranched polyethyleneimine (PEI) films decorated with palladium nanoparticles have been used as efficient catalysts for a series of Suzuki reactions in a lab-on-a-chip format.

Metal and metal-oxide nanostructures and nanoparticles are often key features in materials used in separation technology, biomedical devices, and catalysis.1,2 Poor mechanical strength and a tendency to aggregate, thus reducing the surface to volume ratio, both limit their use in real-time applications.3,4 To overcome these shortcomings, nanoparticles are often dispersed in a matrix, such as sol–gel, biopolymers, and carbon-based materials without disturbing their innate properties at nano-scale level.5,6 Functionalized polymers have been explored extensively in this regard due to their robustness, low cost, ease of handling, and their amenability for chemical modification.7–9Recently, we have demonstrated the immobilization of hyperbranched polyethyleneimine (PEI) hydrogels on metallic surfaces for use as antifouling surfaces.10 Owing to their hydrogelation properties, polymers of this type have proven useful in therapeutic applications, for e.g. bio-mineralization, and the formation of nanostructures.11,12 PEI is a hyperbranched polymer containing very high densities of primary, secondary and tertiary amines, in a 1 : 2 : 1 ratio, and are capable of coordination with transition metals to form nanostructures.13,14 Recent reports on amine functionalized polymer-supported heterogeneous catalysts for C–C coupling reactions (Table 1-SI) prompted us to deploy PEI as a matrix for synthesizing surface-bound palladium nanoparticles for use as catalysts of C–C coupling reactions. For catalytic applications, a miniaturized microfluidic setup, such as a lab-on-a-chip device, can significantly reduce the consumption of chemicals, catalysts, process time and be beneficial for on-site analysis.15,16In this study, we demonstrate the use of the PEI surface-supported nanoparticles for as a support for catalysis of the Suzuki reaction the possibility for using of these Pd-nanoparticle immobilized PEI-derivatized gold surfaces for performing Suzuki reactions in a microfluidics device. Catalytic surface fabrication (Scheme 1) was performed using gold sputtered quartz surfaces (Au/quartz) that were functionalized with 11-mercaptoundecanoic acid (MuDA), and then activated and derivatization with PEI. The polymer attachment was carried out at high ionic strength (150 mM NaCl), which has been found to enhance the thickness and growth of PEI brush-like structures.10 Optimization of the Pd nanoparticle synthesis procedure was performed by varying incubation times and Pd(OAc)2 concentrations (Table 1-SI). A quartz crystal microbalance (QCM) was used to monitor the amount of Pd deposited on the PEI coated Au/quartz resonators.Open in a separate windowScheme 1Palladium immobilization on polyethyleneimine coated Au/quartz surfaces.The energy dispersive X-ray (EDX) spectrum confirmed the presence of Pd in the PEI film with a distinct band at 2.8 keV (Fig. 1A). XPS spectra of the Pd-bound PEI surfaces revealed the presence of the anticipated proleptic elements (C1s, N1s, O1s, Pd3d and Au4f) (Fig. 1A-SI). Deconvoluted peaks differentiated the amine N of PEI (399.8 eV) from that of the amide N (–*N–C Created by potrace 1.16, written by Peter Selinger 2001-2019 O–, 400.8 eV) (Fig. 1B-SI).17,18 Bands around 335 and 340 eV in the survey spectra correspond to the 3d5/2 and 3d3/2 states of the surface bound Pd.19 The deconvoluted bands at 335.3 and 338.2 demonstrated the presence of Pd(0) and Pd(ii), respectively (Fig. 1B). Importantly, peak integration showed the immobilized Pd to be predominantly in the Pd(0) state, with less than 5% present as Pd(ii).19Open in a separate windowFig. 1(A) Energy dispersive X-ray (EDX) analysis and (B) X-ray photoelectron spectra (XPS) of the palladium nanoparticle immobilized PEI coated Au/quartz surface.RAIR spectra confirmed the presence of the PEI on the gold surface based on the discernible vibrational bands of the –N–H–, –CH– and –CN– bending modes of the adsorbed PEI film (Fig. 2). Subtle differences can be observed in the RAIR spectra of the PEI before and after Pd immobilization. The band corresponding to –N–H– bending mode has been significantly red shifted emphasizing the interaction of the Pd particles with the amine moieties of the PEI film (Fig. 2, inset). This, together with the XPS data, provides evidence for the reduction of Pd(ii) to Pd(0) and its incorporation as nanoparticles into the PEI brush layer.Open in a separate windowFig. 2RAIR spectra of PEI coated Au/quartz surface before and after Pd immobilization.SEM images (Fig. 3) showed uniform long-range coating of the palladium nanoparticles on the PEI immobilized surface (PEI/Pd). The crystallinity of the Pd coated PEI surface was evaluated with powder diffraction measurements which showed characteristic peaks for Pd(111), Pd(200) and Pd(220) with Miller indices of 40, 47.2 and 68.3° (JCPDS No. 98-004-7386), respectively, again confirming the presence of Pd nanoparticles in the (0) oxidation state (curve a, Fig. 2-SI).Open in a separate windowFig. 3Scanning electron micrographs of (A) gold surface, (B) polyethyleneimine (PEI) film and (C) PEI-supported palladium particles fabricated on Au/quartz surfaces.The possibility of using these surfaces for catalysis of the Suzuki reaction was explored using a series of phenylboronic acids and substituted aryl halides (). The amount of catalytic nanopalladium loaded was determined by QCM. Au/quartz surfaces coated with PEI/Pd were immersed in the reaction mixtures at 55 °C for 12 h (Section 1.7-SI). Reactions of aryl halides with a series of arylboronic acids offered the corresponding products in good to excellent yield (). This negligible effect on Pd catalyst poisoning confirms the nature of the catalytic Pd exists predominantly in the (0) oxidation state.20 No biphenyl product has been observed when the Suzuki reaction was performed in presence of unmodified Au/quartz surface (without PEI and Pd).Suzuki cross-coupling reactions of aryl halides with arylboronic acids using PEI/Pd as catalystsa
EntryR1XR2Isolated yieldTON × 103
1HIH93%3.1 × 103
2HBrH95%3.4 × 103
3HI2-CH382%2.2 × 103
4HI3-OCH357%1.5 × 103
5HI4-OCH384%2.4 × 103
6HI2-CN15%0.4 × 103
7HI4-CN95%2.8 × 103
84-CH3BrH88%1.5 × 103
94-OCH3BrH95%1.2 × 103
10HI3-NH2n.r.
11HClH94%10.0 × 103
124-OCH3ClH80%5.3 × 103
134-COCH3ClHn.r.
Open in a separate windowaGeneral procedure: 1.0 mmol of aryl halide, 1.2 mmol of arylboronic acid, 2.0 mmol of K2CO3, in H2O/EtOH. Turnover number TON = mol product/mol Pd. n.r. = no reaction.The Suzuki reaction of phenyl iodide and phenyl boronic acid was also performed using shorter reaction times (6 h and 2 h), with the shorter time providing the product in an acceptable 84% and 78% yield respectively (Tables 2 and 3-SI).To assess the stability of the surfaces and the potential for their reuse, the surfaces were removed from the reaction mixtures and the amount of residual Pd was determined by QCM. XPS measurements revealed no significant change on the nature of the immobilized Pd (335.26 and 340.58 eV) (Fig. 3-SI), and as reflected in the ratio of the Pd3d and Au4f bands measured before (0.45) and after (0.44) the reaction () with peaks for Pd(111), Pd(200) and Pd(220) comparable to those before reaction. The SEM and EDX measurements revealed that the nanopalladium had remained immobilized on the PEI matrix (Fig. 4-SI). The amount of residual Pd was again determined by QCM after use of the surfaces in a series of reactions (
EntryRunConc. of Pd, μgIsolated yieldTON
11st±2.393%4.2 × 103
22nd±2.2289%4.1 × 103
33rd±2.2285%4.0 × 103
44th±2.1580%3.8 × 103
Open in a separate windowaGeneral procedure: 1.0 mmol of aryl halide, 1.2 mmol of arylboronic acid, 2.0 mmol of K2CO3, in H2O/EtOH. TON = mol product/mol.The long-term stability of the catalyst surfaces was studied by storing freshly prepared surfaces in water (Milli-Q grade water, 18.2 MΩ, UHP grade N2) for three months after which catalytic activity was determined (93%).We then explored the use of these surfaces in a lab-on-a-chip format by using them in a QCM instrument fitted with a microfluidics liquid delivery system, where the Suzuki reaction of phenyl iodide and phenylboronic acid was examined under flow injection analysis conditions. The reactants were introduced into the 2 μL volume microreactor using the instrument''s peristaltic pump, and the temperature of the reaction was maintained at 40 °C. Formation of the biphenyl product was confirmed by HPLC analysis of the effluent (Fig. 5-SI).In comparison with other reported heterogeneous catalysts for the Suzuki reaction (Table 4-SI), the Pd/PEI surfaces presented here have significantly lower Pd loadings (>0.001 mol%) though comparable performance, highlighting the role of the PEI matrix for facilitating mass transfer of substrates and products to and from the catalytic centers, and for avoiding aggregation of the Pd.  相似文献   
74.
Which heart failure patients profit from natriuretic peptide guided therapy? A meta‐analysis from individual patient data of randomized trials          下载免费PDF全文
Hans‐Peter Brunner‐La Rocca  Luc Eurlings  A. Mark Richards  James L. Januzzi  Matthias E. Pfisterer  Ulf Dahlström  Yigal M. Pinto  Patric Karlström  Hans Erntell  Rudolf Berger  Hans Persson  Christopher M. O'Connor  Deddo Moertl  Hanna K. Gaggin  Christopher M. Frampton  M. Gary Nicholls  Richard W. Troughton 《European journal of heart failure》2015,17(12):1252-1261
  相似文献   
75.
Recipient FK506 pretreatment regimens in rat small bowel transplantation: allograft survival, function, and systemic infection     
Guo WH  Tian L  Yuen ZW  Chan KL  Wo JY  Nicholls G  Dallman M  Tam PK 《Journal of pediatric surgery》2000,35(11):1600-1605
PURPOSE: Successful small bowel transplantation requires effective immunosuppression that preserves intestinal function but avoids opportunistic infection. This study aims to evaluate FK506 as a single immunosuppressant in different pretreatment regimens in a rat high responder strain combination. METHODS: Lewis --> DA rat heterotopic small bowel transplantation was performed. Studied groups were (1) untreated control, n = 12; (2) FK-1, n = 8; (3) FK-3, n = 8. FK506 (2 mg/kg/d, intramuscularly) was given to the recipients for 1 day (FK-1) and 3 days (FK-3) before small bowel transplantation, followed by 2 weeks of subtherapeutic treatment (0.3 mg/kg/d, intramuscularly) after small bowel transplantation. Syngeneic small bowel transplantation also was performed (n = 8). FK blood levels, maltose absorption test, histology, and bacteriology were performed at different postoperative days. RESULTS: Allograft survival was prolonged significantly with FK pretreatment, being more so in FK-3 group (FK-1, 22.2 +/- 1.5 d; FK-3, 40.7 +/- 14.1 d; control, 6.6 +/- 0.8 d; P< .01). In the first postoperative week, FK blood level was significantly higher in FK-3 group (19.8 +/- 1.5 ng/mL) than in FK-1 group (5.0 +/- 0.4 ng/mL; P < .05). There was no evidence of systemic infection in either FK-treated group. For maltose absorption, control allograft was abnormal on day 7 correlating to severely damaged intestinal architecture. In contrast, FK-treated allografts showed well-protected intestinal structure and normal absorption on days 7 and 21. CONCLUSION: High FK506 blood levels in the first postoperative week, achieved with FK pretreatment, prolonged intestinal allograft survival and preserved intestinal structure and function without allowing systemic infection.  相似文献   
76.
Peripheral nerve compression syndromes of the upper limb     
Kate Nicholls  Nicholas D. Furness 《Surgery (Oxford)》2019,37(5):288-293
Nerve compression syndromes are commonly encountered in the elective out-patient setting and therefore core and specialist trainees should understand the aetiology, pathophysiology, investigation and treatment. A knowledge of nerve physiology and clinical assessment of upper limb neurology may be encountered in the MRCS exam.  相似文献   
77.
The Elag-Koln automatic blood pressure recorder. A clinical appraisal.          下载免费PDF全文
L E Ramsay  M G Nicholls  P Boyle 《Heart (British Cardiac Society)》1977,39(7):795-798
The performance of an Elag-Koln semiautomatic blood pressure recorder was compared with the London School of Hygiene mercury sphygmomanometer in 24 subjects providing a wide range of blood pressure measurements. Readings with the two instruments correlated highly (for systole, r=0-99; for diastole phase 4, r=0-97; for diastole phase 5,r=0-98), and the slopes of the regressions did not differ significantly from unity. Elag-Koln measurements were higher for systole (mean difference 3-7 mmHg,P less than 0-001) and diastole phase 5 (mean difference 7-4 mmHg,P less than 0-001), but agreed closely with diastole phase 4 readings with the London School of Hygiene instrument. The Elag-Koln recorder tested was compact, easy to use, and had acceptable accuracy. This type of instrument deserves further testing to examine its suitability for general use.  相似文献   
78.
Can CMR Elucidate the Cardiovascular Benefit of SGLT2 Inhibitors?     
Stephen J. Nicholls  Nitesh Nerlekar 《JACC: Cardiovascular Imaging》2021,14(6):1174-1176
  相似文献   
79.
Comparison of nasopharyngeal flocked swabs and aspirates for rapid diagnosis of respiratory viruses in children.   总被引:3,自引:0,他引:3  
K H Chan  J S M Peiris  W Lim  J M Nicholls  S S Chiu 《Journal of clinical virology》2008,42(1):65-69
BACKGROUND: The quality of clinical specimens is a crucial determinant for virological diagnosis. OBJECTIVES: We compared the viral diagnostic yield for influenza A and respiratory syncytial virus (RSV) from the recently developed nasopharyngeal flocked swabs (NPFS) with nasopharyngeal aspirates (NPA) collected in parallel from 196 hospitalized children with acute respiratory infection during the peak period of influenza A and RSV activity in Hong Kong. Specimens were tested by RT-PCR for influenza A and RSV and viral load determined. They were also tested by direct immunofluorescence (DIF) for influenza A and B, RSV, parainfluenza types 1-3 and adenovirus. RESULTS: Both NPA and NPFS had excellent sensitivity (100%) for detecting influenza A by RT-PCR but NPA was slightly more sensitive than NPFS for detecting RSV by both RT-PCR (100% vs. 92.3%) and DIF (87.2% vs. 84.6%) and for detecting influenza A by DIF (90.2% vs. 82.9%). Viral load for influenza A in NPA and NPFS was not significantly different but that for RSV was higher in NPA. CONCLUSION: NPA remains the optimal specimen for diagnosis of respiratory infections by RT-PCR and DIF. However, collection of NPFS is easier to perform in an out-patient setting, was more acceptable to parents and less likely to generate aerosols than NPA engendering potentially less infection control hazard.  相似文献   
80.
Characterization and clinical application of human CD34+ stem/progenitor cell populations mobilized into the blood by granulocyte colony-stimulating factor   总被引:13,自引:0,他引:13  
Gordon MY  Levicar N  Pai M  Bachellier P  Dimarakis I  Al-Allaf F  M'Hamdi H  Thalji T  Welsh JP  Marley SB  Davies J  Dazzi F  Marelli-Berg F  Tait P  Playford R  Jiao L  Jensen S  Nicholls JP  Ayav A  Nohandani M  Farzaneh F  Gaken J  Dodge R  Alison M  Apperley JF  Lechler R  Habib NA 《Stem cells (Dayton, Ohio)》2006,24(7):1822-1830
  相似文献   
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