Synthesis of novel tri- and tetrasubstituted C<Subscript>18</Subscript> furan fatty esters

A methylene-interrupted C₁₈ keto-acetylenic fatty ester (methyl 12-oxo-9-octadecynoate) was obtained from methyl ricinoleate by bromination-dehydrobromination followed by oxidation. Reaction of methyl 12-oxo-9-octadecynoate with bis(benzonitrile) palladium(II) chloride, allyl bromide, or methyl-allyl bromide furnished methyl 8-[5-hexyl-3-allyl-furan-2-yl]-octanoate (1, 56%) or methyl 8-[5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (2, 55%). Reaction of methyl 12-oxo-11-chloro-or 11-fluoro-9-octadeyynoate (prepared from methyl santalbate-methyl 11-E-9-octadecynoate, found in sandalwood, Santalum album, seed oil) with bis(benzonitrile) palladium(II) chloride gave methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (3, 50%) or methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (4, 50%), respectively. And when methyl 12-oxo-11-chloro- or 11-fluoro-9-octadecynoate was treated with a mixture of bis(benzonitrile) palladium(II) chloride, allyl bromide, or methyl-allyl bromide, the reaction yielded tetrasubstituted C₁₈ furan derivatives, viz, methyl 8-(3-allyl-4-chloro-5-hexyl-furan-2-yl)-octanoate (5, 54%), methyl 8-[4-chloro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl)-octanoate (6, 54%), methyl 8-(3-allyl-4-fluoro-5-hexyl-furan-2-yl]-octanoate (7, 10%), and methyl 8-[4-fluoro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (8, 10%). The presence of a fluorine atom in the furan derivatives 4, 7, and 8 was readily characterized by the appearance of doublets for carbon nuclei, which were coupled to the fluorine atom in the ¹³C NMR spectra. All furan fatty derivatives from this work were characterized by NMR spectroscopic and mass spectrometric analyses. The yields of compounds 7 and 8 were very low (10%) despite attempts to improve the procedure by increasing the amounts of the reactants and catalyst.     

Ölveredelung: Produkt-, Energie-, Prozeß- und Umweltdaten,Ergebnisse von Großanlagen

Oil Refining: Data on Product, Energy, Process, Environmental Pollution, and Processing Data from Large Technical Plants The need to develope new methods for processing new raw materials, meeting wider market demands, conserving energy and providing environmental protection is discussed. Physical refinement provides the means to accomplish these ends, as well as being the only practical way to overcome certain new problems such as contamination with pesticides. Modern steam distillation equipment is flexible enough to handle a wide range of energy usage, recovering the fatty acids in a directly useable form without use of lye and soapstock splitting, and with very low oil losses. Data is provided to show the extreme economy of one particular method versus other physical refining equipment, and to give information on the product quality. A formula is presented to prove the reality of the low stripping steam usage achieved in practice.     

Mass spectrometric immunoassay and MRM as targeted MS-based quantitative approaches in biomarker development: Potential applications to cardiovascular disease and diabetes

Type 2 diabetes mellitus (T2DM) is an important risk factor for cardiovascular disease (CVD)—the leading cause of death in the United States. Yet not all subjects with T2DM are at equal risk for CVD complications; the challenge lies in identifying those at greatest risk. Therapies directed toward treating conventional risk factors have failed to significantly reduce this residual risk in T2DM patients. Thus newer targets and markers are needed for the development and testing of novel therapies. Herein we review two complementary MS-based approaches—mass spectrometric immunoassay (MSIA) and MS/MS as MRM—for the analysis of plasma proteins and PTMs of relevance to T2DM and CVD. Together, these complementary approaches allow for high-throughput monitoring of many PTMs and the absolute quantification of proteins near the low picomolar range. In this review article, we discuss the clinical relevance of the high density lipoprotein (HDL) proteome and Apolipoprotein A-I PTMs to T2DM and CVD as well as provide illustrative MSIA and MRM data on HDL proteins from T2DM patients to provide examples of how these MS approaches can be applied to gain new insight regarding cardiovascular risk factors. Also discussed are the reproducibility, interpretation, and limitations of each technique with an emphasis on their capacities to facilitate the translation of new biomarkers into clinical practice.     

Evolution of the cranial computed tomography scan in child abuse

Computed tomography (CT) scans obtained at the time of clinical presentation have occasionally been reported to be normal in children with history and findings of significant abusive head injury. We have retrospectively observed abnormalities in "normal" scans of some similar children. We have also seen abnormalities develop on serial scanning. To determine how frequently these situations occur, we reviewed charts of 34 children with a final diagnosis of child abuse who also had cranial CT scans performed. Their CT scans were retrospectively reviewed by a pediatric radiologist. Eleven (11/34) CT scans had initially been interpreted as normal. Four (4/11) of these had been reinterpreted during the hospitalization as abnormal, affecting medical (1) and legal (3) outcome. Repeat scanning in three of the remaining seven resulted in surgical drainage of a subdural effusion (1) and affected legal outcome (2). Four of the seven initial scans felt normal throughout the hospitalizations were judged abnormal on retrospective review. This evaluation was confirmed in the two rescanned. Initial CT interpretation most often failed to appreciate changes in parenchymal density and small amounts of falcine or cortical subdural blood. Subsequent scans also showed evolving effusions and infarcts. Changes were noted in 1 1/2 to 5 days. The CT scan frequently shows subtle changes in the immediate posttrauma period. If the child does not recover promptly, subsequent scans frequently result in significant changes in clinical and legal management.     

Evidence that human cardiac allograft acceptance is associated with a decrease in donor-reactive helper T lymphocytes

We have reported that acute cardiac allograft rejection is associated with increased numbers of donor-reactive helper T lymphocytes (HTL) in the peripheral blood of patients. Further, increased frequencies of circulating donor-reactive HTL may predict allograft rejection episodes diagnosed by endomyocardial biopsy. The present study evaluates the relationship between donor-reactive HTL and allograft "acceptance" in cardiac transplant recipients bearing long-term allografts (> 1 year). Patients were categorized as either long-term acceptors or persistent rejecters based on the number of rejection episodes and the ability to withdraw steroid therapy. Limiting dilution analysis for IL-2-producing HTL was utilized, with cadaver donor splenocytes as a source of donor alloantigens. Donor-reactive HTL frequencies were determined from peripheral blood samples obtained before transplant, and at 1 month and 1 year after transplant. Individuals who accommodated their allografts and were withdrawn from steroid therapy had reduced numbers of donor-reactive HTL at 1 year after transplant as compared with earlier time points. Further, PBMC obtained from these individuals at 1 year after transplant responded weakly to donor alloantigens in a mixed lymphocyte response (MLR). This relationship between donor-reactive HTL and allograft accommodation was exemplified in a cardiac/liver transplant patient who was diagnosed with progressive multifocal leukoencephalopathy and removed from all immunosuppression. No subsequent rejection episodes were diagnosed. Donor-reactive HTL were not detectable and this individual failed to mount an MLR to donor alloantigens. However, a vigorous donor-reactive response was observed when MLR cultures were supplemented with exogenous IL-2. Therefore, nonresponsiveness to the allograft appeared to be due to a deficit in IL-2 production. In contrast, patients who experienced persistent rejection episodes and required continued steroid therapy maintained large numbers of donor-reactive HTL at 1 year after transplant. PBMC from these individuals responded vigorously to donor alloantigens in an MLR. Hence, monitoring donor-reactive HTL may identify individuals who have accommodated their graft and may tolerate a reduction in immunosuppression.     

Symptomatic subclavian steal syndrome four decades after operation for dysphagia lusoria

Congenital abnormalities of the aortic arch may lead to signs and symptoms of tracheal and esophageal obstruction secondary to a restrictive vascular ring. There are many case reports and monographs concerning the surgical management of dysphagia lusoria. This case provides the first example of long-term follow-up of surgical intervention for relief of dysphagia lusoria. A 45-year-old laborer presented with a several year history of episodic bilateral blindness and a more recent onset of "drop attacks." Notably this patient had presented at the age of 18 months with difficulty breathing and eating since birth. The patient also had frequent upper respiratory infections and episodes of pneumonia. Workup revealed a right-sided aortic arch with a left ligamentum arteriosum. When he was first seen in our clinic, history and physical examination revealed claudication and diminished pulses in the left upper extremity. Arteriography and duplex studies confirmed reversal of flow in the patient's left vertebral artery. The arteriogram demonstrated the presence of a right-sided aortic arch and descending aorta along with the proximal stump of the previously ligated left subclavian artery. He underwent left carotid to left axillary artery bypass for the treatment of symptomatic subclavian steal syndrome. His symptoms have resolved with return of antegrade vertebral flow and the presence of normal pulses in the left arm. Congenital aortic abnormalities that lead to tracheal and esophageal compromise are numerous and varied. Surgical management requires a thorough understanding of the person's anatomy and preoperative planning. The life expectancy of patients with dysphagia lusoria necessitates consideration of the long-term consequences of surgical intervention.     

Laser-Printed Plasmonic Metasurface Supporting Bound States in the Continuum Enhances and Shapes Infrared Spontaneous Emission of Coupled HgTe Quantum Dots

In order to advance the development of quantum emitter-based devices, it is essential to enhance light-matter interactions through coupling between semiconductor quantum dots with high quality factor resonators. Here, efficient tuning of the emission properties of HgTe quantum dots in the infrared spectral region is demonstrated by coupling them to a plasmonic metasurface that supports bound states in the continuum. The plasmonic metasurface, composed of an array of gold nanobumps, is fabricated using single-step direct laser printing, opening up new opportunities for creating exclusive 3D plasmonic nanostructures and advanced photonic devices in the infrared region. A 12-fold enhancement of the photoluminescence in the 900–1700 nm range is observed under optimal coupling conditions. By tuning the geometry of the plasmonic arrays, controllable shaping of the emission spectra is achieved, selectively enhancing specific wavelength ranges across the emission spectrum. The observed enhancement and shaping of the emission are attributed to the Purcell effect, as corroborated by systematic measurements of radiative lifetimes and optical simulations based on the numerical solution of Maxwell's equations. Moreover, coupling of the HgTe photoluminescence to high quality factor modes of the metasurface improves emission directivity, concentrating output within an ≈20° angle.     

The unanticipated difficult airway with recommendations for management

PURPOSE: To review the current literature and generate recommendations on the role of newer technology in the management of the unanticipated difficult airway. METHODS: A literature search using key words and filters of English language and English abstracted publications from 1990-96 contained in the Medline, Current Contents and Biological Abstracts databases was carried out. The literature was reviewed and condensed and a series of evidence-based recommendations were evolved. CONCLUSIONS: The unanticipated difficult airway occurs with a low but consistent incidence in anaesthesia practice. Difficult direct laryngoscopy occurs in 1.5-8.5% of general anaesthetics and difficult intubation occurs with a similar incidence. Failed intubation occurs in 0.13-0.3% general anaesthetics. Current techniques for predicting difficulty with laryngoscopy and intubation are sensitive, non-specific and have a low positive predictive value. Assessment techniques which utilize multiple characteristics to derive a risk factor tend to be more accurate predictors. Devices such as the laryngeal mask, lighted stylet and rigid fibreoptic laryngoscopes, in the setting of unanticipated difficult airway, are effective in establishing a patient airway, may reduce morbidity and are occasionally lifesaving. Evidence supports their use in this setting as either alternatives to facemask and bag ventilation, when it is inadequate to support oxygenation, or to the direct laryngoscope, when tracheal intubation has failed. Specifically, the laryngeal mask and Combitube have proved to be effective in establishing and maintaining a patent airway in "cannot ventilate" situations. The lighted stylet and Bullard (rigid) fibreoptic scope are effective in many instances where the direct laryngoscope has failed to facilitate tracheal intubation. The data also support integration of these devices into strategies to manage difficult airway as the new standard of care. Training programmes should ensure graduate physicians are trained in the use of these alternatives. Continuing medical education courses should allow physicians in practice the opportunity to train with these alternative devices.     

An integrated dual sensor system automatically optimized by target rate histogram

The use of combined sensors and advanced algorithms using different principles can improve rate performance over a single sensor system. Combinations of sensors and more sophisticated algorithms, however, invariably increase the complexity of pacemaker programming. An automatically optimized combined minute ventilation and activity DDDR pacemaker was developed to minimize repeated sensor adjustment. The device used subthreshold (below cardiac stimulation threshold) lead impedance to detect lead configuration at implantation automatically, followed by "implant management," including setting of lead polarity and initiation of DDDR pacing. Automatic sensor adaptation was achieved by programming a "target rate histogram" based on the patient's activity level and frequency of exertion, and the rate profile optimization process matched the recorded integrated sensor response to the target rate histogram profile. In nine patients implanted with the DX2 pacemakers, the implant management gave 100% accuracy in the detection of lead polarity. Rate profile optimization automatically increased the pacing rate during exercise between discharge and 3-month follow-up (hall walk: 78 +/- 3 vs 98 +/- 3 beats/min, and maximal treadmill exercise: 89 +/- 6 vs 115 +/- 5 beats/min, P < 0.001) with a significant increase in exercise duration during maximal exercise (7.18 +/- 1 min vs 9.56 +/- 2 min, P = 0.05). The accuracy of rate profile optimization versus manual programming was assessed at 1 month, and there was no significant difference between pacing rate kinetics and maximal pacing rate between the two methods of programming. In conclusion, pacemaker automaticity can be initiated at implantation and the self-optimized rate adaptive response appeared to be comparable to that derived from a manual programming procedure, which may reduce the need to perform time consuming sensor programming.