Optimizing Thermal-Optical Methods for Measuring Atmospheric Elemental (Black) Carbon: A Response Surface Study

The chemical, physical, and morphological complexity of atmospheric aerosol elemental carbon (EC) presents major problems in assuring measurement accuracy. Since EC and black carbon are often considered equivalent, methods based on thermal-optical analysis (TOA) are widely used for EC in ambient air samples because no prior knowledge of the aerosol's absorption coefficient is required. Nevertheless, different TOA thermal desorption protocols result in wide EC-to-total-carbon (TC) variation. We created three response surfaces with the following response variables: EC/TC, maximum laser attenuation in the He phase ( L max ), and laser attenuation at the end of the He phase ( L He4 ). A two-level central-composite factorial design comprised of four factors considered the temperatures and durations of all desorption steps in TOA's inert (He) phase and the initial step in TOA's oxidizing (O 2 -He) phase. L max was used to assess the positive bias caused by nonvolatile unpyrolized organic carbon (OC char) being measured as native EC. A negative bias that the attenuated laser response does not detect is caused by the loss of native EC in the He phase. L He4 was used as a surrogate indicator for the loss of native EC in the He phase. The intersection between the L max and L He4 surfaces revealed TOA conditions where both the production of OC char in the He phase was maximized and the loss of native EC in the He phase was minimized, therefore leading to an optimized thermal desorption protocol. Based on the sample types used in this study, the following are generalized optimal conditions when TOA is operated in the fixed-step-durations, laser-transmission mode (i.e., TOT): step 1 in He, 190°C for 60 s; step 2 in He, 365°C for 60 s; step 3 in He, 610°C for 60 s; step 4 in He, 835°C for 72 s. For steps 1-4 in O 2 -He, the conditions are 550°C for 180 s, 700°C for 60 s, 850°C for 60 s, and 900°C for 90 s to 120 s, respectively.     

Absence of detectable human herpesvirus 8 in the semen of human immunodeficiency virus-infected men without Kaposi's sarcoma

The prevalence of human herpesvirus 8 (HHV-8)/Kaposi's sarcoma (KS)-associated herpesvirus was investigated in the semen of 99 human immunodeficiency virus (HIV)-infected men (median CD4 cell count, 357/mm3) by use of a polymerase chain reaction (PCR) assay capable of detecting <10 copies of HHV-8 DNA. Of the subjects, 95 (96%) self-identified as men who have sex with men (MSM), and 3 had a history of clinical KS. Seminal cell specimens were negative for HHV-8 in 98 subjects. None of the 26 without KS (27.1% of 96 tested) who were seropositive for HHV-8 by IFA for latency-associated nuclear antigens had HHV-8 detected in their semen. The only subject with any evidence for seminal HHV-8 DNA was seropositive for HHV-8 and had active KS. HHV-8 was detected in 10 (10.4%) of 96 peripheral blood mononuclear cell specimens. The prevalence of HHV-8 DNA by PCR in semen of HIV-infected MSM without KS is low.     

Testing a mathematical model for initial chemical reaction fouling using a dilute protein solution

A 1 wt% lysozyme solution was used as a model fluid to test a previously formulated mathematical model for the initial chemical reaction fouling rate of a heat transfer surface. The experimental results showed that, at a given wall temperature, a maximum initial fouling rate existed over a range of fluid velocities. The maximum rate and the fluid velocity at which it occurred both increased as the wall temperature increased. These observations were consistent with the model. Quantitatively, the average absolute percent deviation between the experimental results and the optimum model predictions was 23,3%. The decrease in initial fouling rate with increasing velocity at high fluid velocities was even greater than predicted by the model.     

Structural modeling of the pro-ocytocin-neurophysin precursor

The hormonal precursor pro-ocytocin-neurophysin is activated by selectivecleavage at Arg2-Ala13, producing mature ocytocin and neurophysin. Tounderstand the cleavage mechanism better, and in particular the recognitionof the cleavage site, it is necessary to characterize the three-dimensionalstructure of the precursor molecule. Here we combine a variety ofexperimental data with molecular modeling and dynamics calculations toderive possible precursor conformations. In the models obtained, theN-terminus of the precursor, corresponding to the ocytocin segment, ishydrogen bonded in a pocket of the neurophysin moiety in a similar mannerto a crystallographically obtained non-covalent complex between the twomolecules. The calculations suggest that although the ocytocin segment isrelatively flexible, it adopts a stable, broad loop structure in thevicinity of the cleavage region, which may constitute the structuralelement recognized by the cleaving enzyme. The calculations also suggest apossible widening of the distance between the two neurophysin domains inthe precursor relative to that in the non-covalent neurophysin- ocytocincomplex.     

Interactions between immunoglobulin-like and catalytic modules in Clostridium thermocellum cellulosomal cellobiohydrolase CbhA

Cellobiohydrolase CbhA from Clostridium thermocellum cellulosome is a multi-modular protein composed starting from the N-terminus of a carbohydrate-binding module (CBM) of family 4, an immunoglobulin(Ig)-like module, a catalytic module of family 9 glycoside hydrolases (GH9), X1(1) and X1(2) modules, a CBM of family 3 and a dockerin module. Deletion of the Ig-like module from the Ig-GH9 construct results in complete inactivation of the GH9 module. The crystal structure of the Ig-GH9 module pair reveals the existence of an extensive module interface composed of over 40 amino acid residues of both modules and maintained through a large number of hydrophilic and hydrophobic interactions. To investigate the importance of these interactions between the two modules, we compared the secondary and tertiary structures and thermostabilities of the individual Ig-like and GH9 modules and the Ig-GH9 module pair using both circular dichroism (CD) spectroscopy and differential scanning calorimetry (DSC). Thr230, Asp262 and Asp264 of the Ig-like module are located in the module interface of the Ig-GH9 module pair and are suggested to be important in 'communication' between the modules. These residues were mutated to alanyl residues. The structure, stability and catalytic properties of the native Ig-GH9 and its D264A and T230A/D262A mutants were compared. The results indicate that despite being able to fold relatively independently, the Ig-like and GH9 modules interact and these interactions affect the final fold and stability of each module. Mutations of one or two amino acid residues lead to destabilization and change of the mechanism of thermal unfolding of the polypeptides. The enzymatic properties of native Ig-GH9, D264A and T230A/D262A mutants are similar. The results indicate that inactivation of the GH9 module occurs as a result of multiple structural disturbances finally affecting the topology of the catalytic center.     

Development of a methodology for characterizing commercial chlorinated latex gloves

Chlorination of gloves has gained popularity as a more permanent method of reducing the inherent tackiness of natural rubber latex compared to using powder as a dusting lubricant. Transmission of proteins in natural rubber latex into the air as a result of using powder on natural rubber latex gloves may cause serious complications to allergic individuals. A methodology for characterizing commercial chlorinated natural rubber latex gloves using a combination of attenuated total reflectance (ATR)–Fourier transform infrared (FTIR) spectroscopy and ion chromatography (IC) is described. ATR–FTIR studies established that 930–915 and 670–650 cm⁻¹ are definitive wavenumber ranges for the identification of chlorine in commercial chlorinated latex gloves. Confirmation of the ATR–FTIR results and semiquantification of the chlorine content in the latex gloves was carried out by the IC technique. This methodology can be used by glove manufacturers to determine the amount of chlorine in batches of commercial gloves, and thereby prevent possible threats to public health arising from the deterioration of surgical and examination chlorinated latex gloves under severe storage conditions before the end of their expected shelf life. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 672–682, 2001     

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.     

Ecosystem matters: fish consumption, mercury intake and exposure among fluvial lake fish-eaters

Many studies use the number of fish meals as an estimate of Hg intake, although fish Hg concentrations, even within the same species, can greatly vary. Furthermore, most freshwater advisories only refer to local catch, while market fish advisories only focus on market fish, although both can contribute to Hg body burden. The present study, carried out in lakeside communities from 2 ecosystems in Quebec, Canada, sought to (i) estimate Hg intake from local freshwater sources, hunted waterfowl and market fish and seafood, and (ii) examine the relations between fish consumption, estimated Hg intake and biomarkers of exposure. A total of 238 adults (18-74 years), who had consumed local catch within the past three months, responded to an extensive interview-administered fish and waterfowl frequency questionnaire. Anthropometric measures were taken and a self-administered questionnaire was used to obtain socio-demographic information. Hg intake was estimated as µg Hg/kg body weight/day. Blood and hair samples were analyzed for Hg content. Results showed that persons from one ecosystem ate significantly more fish compared to those from the other (median: 52.1 g/day vs 38.9 g/day), but presented significantly lower concentrations of hair Hg (median: 448.0 ng/g vs 730.5 ng/g), blood organic Hg (median: 1.1 µg/L vs 3.4 µg/L) and inorganic Hg (median: 0.4 µg/L vs 0.8 µg/L). Median daily total Hg intake was 0.080 µg/kg bw/day for the former community and 0.141 µg/kg bw/day for the latter. Overall, 59.5% from the first ecosystem and 41.0% from the other, exceeded the US EPA RfD (0.1 µg/kg bw/day), while 13.2% and 6.0%, respectively, exceeded the Canadian tolerable daily intake (0.47 µg/kg bw/day) for adults. For the two groups, freshwater fish consumption frequency, but not total fish, was positively associated with bioindicators of Hg while estimated Hg intake from freshwater catch as well as from total fish consumption were positively related to Hg biomarkers. There was a positive relation between consumption and estimated Hg intake from freshwater fish and blood inorganic Hg. These findings indicate that the number of fish can be a poor surrogate for Hg exposure. The differences observed here for Hg intake and exposure reflect ecosystem disparities in fish diversity and Hg bioaccumulation. Studies and advisories need to consider Hg fish concentrations and fish-eating patterns in different ecosystems, as well as the contribution of market fish. The relation between fish consumption and inorganic Hg exposure, reported as well in other studies, needs to be further investigated.