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1.
Phys Chem Chem Phys ; 22(15): 8171-8181, 2020 Apr 15.
Article in English | MEDLINE | ID: mdl-32249870

ABSTRACT

Benzaldehyde is a simple aromatic aldehyde and has a wide range of applications in the food, pharmaceutical, and chemical industries. The positive electron affinity of this compound suggests that low-energy electrons can be easily trapped by neutral benzaldehyde. In the present study, we investigated the formation of negative ions following electron attachment to benzaldehyde in the gas-phase. Calculations on elastic electron scattering from benzaldehyde indicate a π* valence bound state of the anion at -0.48 eV and three π* shape resonances (0.78, 2.48 and 5.51 eV). The excited state spectrum of the neutral benzaldehyde is also reported to complement our findings. Using mass spectrometry, we observed the formation of the intact anionic benzaldehyde at ∼0 eV. We ascribe the detection of the benzaldehyde anion to stabilization of the π* valence bound state upon dissociative electron attachment to a benzaldehyde dimer. In addition, we report the cross sections for nine fragment anions formed through electron attachment to benzaldehyde. Investigations carried out with partially deuterated benzaldehyde show that the hydrogen loss is site-selective with respect to the incident electron energy. In addition, we propose several dissociation pathways, backed up by quantum chemical calculations on their thermodynamic thresholds. The threshold calculations also support that the resonances formed at higher energies lead to fragment anions observable by mass spectrometry, whereas the resonances at low electron energies decay only by electron autodetachment.

2.
Phys Chem Chem Phys ; 19(9): 6406-6415, 2017 Mar 01.
Article in English | MEDLINE | ID: mdl-28198894

ABSTRACT

Imidazole [C3H4N2] is ubiquitous in nature as an important biological building block of amino acids, purine nucleobases or antibiotics. In the present study, dissociative electron attachment to imidazole shows low energy shape resonances at 1.52 and 2.29 eV leading to the most abundant dehydrogenated anion [imidazole - H]- through dehydrogenation at the N1 position. All the other anions formed exhibit core excited resonances observed dominantly at similar electron energies of ∼7 and 11 eV, suggesting an initial formation through two temporary negative ion states. Among these anions, multiple dehydrogenation reactions are observed resulting in the loss of 2 up to 4 hydrogens, thus, leading to a complete dehydrogenation of the imidazole molecule, an interesting prototype of complex unimolecular decay induced by the attachment of a single electron. Additionally, the quantum chemical calculations reveal that these multiple dehydrogenation reactions are responsible for the remarkable one electron-induced gas-phase chemistry leading to the opening of the ring. The formation of the observed anions is likely driven by the high positive electron affinity of cyanocarbon molecules supported by quantum chemical calculations. The formation of H- showed additional resonance at about 5 eV and dipolar dissociation above ∼14 eV.


Subject(s)
Electrons , Hydrogen/chemistry , Imidazoles/chemistry , Hydrogenation , Models, Chemical
3.
Aust Vet J ; 94(5): 129-37, 2016 May.
Article in English | MEDLINE | ID: mdl-27113981

ABSTRACT

OBJECTIVES: To develop molecular tools for the investigation of the prevalence, species and faecal shedding of Yersinia in sheep. METHODS: A quantitative PCR (qPCR) targeting the ß subunit of the Yersinia spp. RNA polymerase gene was developed and validated. The prevalence of pathogenic Y. enterocolitica was determined by screening for the virulent yst gene. These qPCR assays were used to determine Yersinia spp. prevalence and faecal shedding concentration from 3412 faecal samples collected from approximately 1189 lambs (100-180 lambs/flock) on eight farms across Australia. This was a longitudinal study, with sheep sampled on three occasions (weaning, post-weaning and pre-slaughter). A subset of up to five positive samples from each sampling on each farm (n = 111) was sequenced. RESULTS: Yersinia spp. (including both pathogenic and non-pathogenic species) were identified in all flocks, with 60.7% of lambs shedding Yersinia spp. on at least one sampling occasion. Point prevalence ranged from 4% to 91% across farms and sampling occasions. Median Yersinia spp. bacterial concentration was 1.1 × 10(6) , 2.8 × 10(6) and 5.6 × 10(5) organisms/g faeces at weaning, post-weaning and pre-slaughter, respectively, across all farms. Pathogenic Y. enterocolitica was identified in all eight flocks sampled, with 14.8% of lambs shedding pathogenic Y. enterocolitica on at least one sampling occasion. CONCLUSION: Yersinia spp. and pathogenic Y. enterocolitica in particular were commonly identified in a sample of Australian sheep flocks using molecular techniques. Further studies into associations between faecal shedding of pathogenic Yersinia spp. and sheep productivity or clinical disease may utilise qPCR in conjunction with other diagnostic tools.


Subject(s)
Sheep Diseases/epidemiology , Yersinia Infections/veterinary , Yersinia/genetics , Animals , Australia , Bacterial Shedding , Feces/microbiology , Female , Longitudinal Studies , Polymerase Chain Reaction/veterinary , Prevalence , Sheep/microbiology , Sheep Diseases/microbiology , Yersinia Infections/epidemiology , Yersinia enterocolitica/genetics
4.
Aust Vet J ; 93(6): 221-4, 2015 Jun.
Article in English | MEDLINE | ID: mdl-26010929

ABSTRACT

OBJECTIVE: To isolate Trichostrongylus vitrinus from naturally-acquired mixed trichostrongylid infections (predominantly Trichostrongylus spp. and Teladorsagia circumcincta) in sheep using differential larval development temperatures and the anatomical location of adults. METHODS: Faeces were collected from ewes with mixed, naturally acquired trichostrongylid infection, and incubated at low temperatures (4°C or 8°C) for 20-68 days depending on temperature. Harvested infective larvae were passaged through worm-free lambs, from which the first 5 m of small intestine was collected and adult worms recovered. Purity of infection with T. vitrinus was assessed by examination of spicules on 100 adult male worms. Eggs of recovered adult female worms were cultured at 25°C and harvested larvae were re-passaged through worm-free lambs. RESULTS: Low temperature incubation (≤8°C) successfully exploited variation in the developmental temperature required by pre-parasitic stages of small intestinal nematodes, allowing T. vitrinus to develop while others did not. Differential organ harvest from infected sheep allowed isolation of T. vitrinus from other gastrointestinal nematodes, with amplification of pure T. vitrinus achieved by passage through a further generation of lambs. CONCLUSION: A successful method for the isolation of pure T. vitrinus from mixed infections is described. The resulting pure strain of T. vitrinus has been amplified and is held by two institutions for use in research (CSIRO reference SARDI 2011 strain).


Subject(s)
Sheep Diseases/parasitology , Sheep/parasitology , Trichostrongylosis/veterinary , Trichostrongylus/isolation & purification , Animals , Eggs , Feces/parasitology , Female , Gastrointestinal Tract/parasitology , Larva , Male , Temperature , Trichostrongylosis/parasitology
5.
Res Vet Sci ; 100: 138-47, 2015 Jun.
Article in English | MEDLINE | ID: mdl-25843895

ABSTRACT

The effects of, and interactions between chronic Trichostrongylus vitrinus infection and immune suppression with methylprednisolone were investigated for a period of 112 days in a grazed flock of 176 crossbred meat lambs. Worm egg count of non-immune-suppressed lambs increased rapidly from days 21 to 42 post-initial infection, and then steadily declined. Infection was associated with significantly decreased fat depth, eye muscle area and cold carcase weight, and increased circulating anti-T. vitrinus IgG and IgA. Immune suppression led to sustained increases in WEC, and significantly greater worm count, liver weight, fat depth and carcase dressing percentage, and significantly reduced IgG and IgA anti-T. vitrinus titres, lymphocyte counts, adrenal weight, eye muscle area and cold carcase weight. Both infection and immune suppression were associated with significant body weight reductions. Only 39% of reduced growth rate due to infection was attributable to the host immune response to T. vitrinus.


Subject(s)
Immunosuppressive Agents/pharmacology , Methylprednisolone/pharmacology , Sheep Diseases/immunology , Trichostrongylosis/veterinary , Trichostrongylus/physiology , Animal Husbandry , Animals , Chronic Disease , Female , Immunosuppression Therapy/veterinary , Male , Random Allocation , Sheep , Sheep Diseases/parasitology , Trichostrongylosis/immunology , Trichostrongylosis/parasitology
6.
J Phys Chem A ; 110(14): 4846-53, 2006 Apr 13.
Article in English | MEDLINE | ID: mdl-16599454

ABSTRACT

The performance of a density functional theory approach in calculating the equilibrium bond length, dipole moment, and harmonic vibrational frequency in a series of group 6 (Cr, Mo, W) transition metal-containing diatomic molecules is evaluated. Using flexible basis sets comprised of Slater type functions, a wide range of exchange-correlation functionals is investigated. Comparing with known experimental values and published results from high-level theoretical calculations, the most suitable functional form is selected. The importance of relativistic effects is checked, and predictions are made for several unknown dipole moments. The best agreement with experimental parameters is obtained when using a general gradient approximation, while special and hybrid functional forms give less accurate results.

7.
J Org Chem ; 71(7): 2870-3, 2006 Mar 31.
Article in English | MEDLINE | ID: mdl-16555844

ABSTRACT

The reduction of dipyridil[3,2-a:2'3'-c]phenazine, dppz, by pulse radiolytically generated e(-)(sol) or by the reaction of the dppz excited states with electron donors produces the radical dppzH(.). The dimer radical, (dppz)(2)H(.), exists in equilibrium with dppz with an association constant, K = 10(3) M(-1). The rate constant for the reaction of dppzH(.) with dppz is k = 4.3 x 10(6) M(-1) s(-1). DFT calculations on the structures of dppzH(.) and the doubly reduced and doubly protonated dppzH(2) rendered a planar structure for the former species and a bent one for the latter.

9.
J Phys Chem A ; 109(3): 461-5, 2005 Jan 27.
Article in English | MEDLINE | ID: mdl-16833366

ABSTRACT

A combined experimental and theoretical approach has been used to probe the radiolytic decomposition of liquid pyridine. The major single condensed phase product in the gamma-radiolysis of pyridine is dipyridyl with a yield of 1.25 molecules/100 eV total energy absorbed. Scavenging studies suggest that most, if not all, dipyridyl has a radical precursor, but only about 10% of that is due to the pyridyl radical. The remainder of the dipyridyl may be due to reaction of the parent radical cation with pyridine. Iodine scavenging and quantum chemical calculations both show that the ortho-pyridyl radical (2-pyridyl) is far more stable than the other two isomers.

10.
Vet Parasitol ; 103(4): 355-65, 2002 Feb 04.
Article in English | MEDLINE | ID: mdl-11777614

ABSTRACT

Sheep of two bloodlines of Merino were artificially infested with equal numbers of lice (Bovicola ovis) and the resulting louse populations were monitored over the following 20 months. The sheep were shorn 6 and 17 months after infestation and, for analysis, the louse counts considered in 3 years separated by shearings. Nematode faecal egg counts (FECs) were assessed on faecal samples collected on five occasions, three times following natural challenge and twice after artificial challenge with 40,000 trichostrongyloid larvae (84% Trichostrongylus vitrinus). In addition, blood samples were collected and measured for B. ovis-specific immunoglobulins (predominantly IgG), B. ovis-specific IgE and serum total IgE. Bloodlines differed significantly in the size of louse populations at the end of year 2, FEC after both natural and artificial challenge and in serum levels of all three antibodies (p<0.05). There were also large variations in louse counts and FEC among sheep within bloodlines. Louse counts at inspections after louse populations had been allowed to build up were highly repeatable, both between and within years. However, correlations with counts at inspections soon after initial infestation and following shearing were lower. FEC after natural challenge was correlated with louse counts in year 2 (r=0.45, p<0.01) and year 3 (r=0.38, p<0.05), but the correlation with counts in year 1 was not significant (r=0.25, p>0.05). FEC following artificial challenge was significantly correlated with louse counts in year 3 (r=0.36, p<0.05), but not in year 2 (r=0.25, p>0.05) or year 1 (r=0.04, p>0.05). Louse counts in the 3 years were significantly correlated with anti-B. ovis antibody concentration (r=0.60, 0.48, 0.36), but not with levels of either anti-B. ovis or total serum IgE. These results suggest that sheep with greater resistance to gastrointestinal parasites also tend to be less susceptible to lice. Whether this is due to interaction of the effects of the parasites or to correlation in underlying resistance mechanisms requires clarification.


Subject(s)
Intestinal Diseases, Parasitic/veterinary , Lice Infestations/veterinary , Phthiraptera/immunology , Sheep Diseases/immunology , Trichostrongyloidea/immunology , Trichostrongyloidiasis/veterinary , Animals , Disease Susceptibility/veterinary , Feces/parasitology , Female , Immunoglobulin E/blood , Immunoglobulin G/blood , Intestinal Diseases, Parasitic/immunology , Lice Infestations/complications , Lice Infestations/immunology , Male , Parasite Egg Count/veterinary , Phthiraptera/growth & development , Seasons , Sheep , Sheep Diseases/parasitology , Trichostrongyloidea/pathogenicity , Trichostrongyloidiasis/immunology , Wool/parasitology
11.
J Am Chem Soc ; 123(20): 4781-91, 2001 May 23.
Article in English | MEDLINE | ID: mdl-11457288

ABSTRACT

The effect of hydroxymethyl conformation (gg, gt, and tg rotamers about the C4-C5 bond) on the conformational energies and structural parameters (bond lengths, bond angles, bond torsions) of the 10 envelope forms of the biologically relevant aldopentofuranose, 2-deoxy-beta-D-erythro-pentofuranose (2-deoxy-D-ribofuranose) 2, has been investigated by ab initio molecular orbital calculations at the HF/6-31G level of theory. C4-C5 bond rotation induces significant changes in the conformational energy profile of 2 (2gt and 2tg exhibit one global energy minimum, whereas 2gg exhibits two nearly equivalent energy minima), and structural changes, especially those in bond lengths, are consistent with predictions based on previously reported vicinal, 1,3- and 1,4-oxygen lone pair effects. HF/6-31G-optimized envelope geometries of 2gg were re-optimized using density functional theory (DFT, B3LYP/6-31G), and the resulting structures were used in DFT calculations of NMR spin-spin coupling constants involving 13C (i.e., J(CH) and J(CC) over one, two, and three bonds) in 2gg according to methods described previously. The computed J-couplings were compared to those reported previously in 2gt to assess the effect of C4-C5 bond rotation on scalar couplings within the furanose ring and hydroxymethyl side chain. The results confirm prior predictions of correlations between 2J(CH), 3J(CH), 2J(CC) and 3J(CC), and ring conformation, and verify the usefulness of a concerted application of these couplings (both their magnitudes and signs) in assigning preferred ring and C4-C5 bond conformations in aldopentofuranosyl rings. The new calculated J-couplings in 2gg have particular relevance to related J-couplings in DNA (and RNA indirectly), where the gg rotamer, rather than the gt rotamer, is observed in most native structures. The effects of two additional structural perturbations on 2 were also studied, namely, deoxygenation at C5 (yielding 2,5-dideoxy-beta-D-erythro-pentofuranose 4) and methyl glycosidation at O1 (yielding methyl 2-deoxy-beta-D-erythro-pentofuranoside 5) at the HF/6-31G level. The conformational energy profile of 4 resembles that found for 2gt, not 2gg, indicating that 4 is an inappropriate structural mimic of the furanose ring in DNA. Glycosidation failed to induce differential stabilization of ring conformations containing an axial C1-O1 bond (anomeric effect), contrary to experimental data. The latter discrepancy indicates that either the magnitude of this differential stabilization depends on ring configuration or that solvent effects, which are neglected in these calculations, play a role in promoting this stabilization.


Subject(s)
Ribosemonophosphates/chemistry , Chemical Phenomena , Chemistry, Physical , Glycosides/chemistry , Magnetic Resonance Spectroscopy , Molecular Conformation , Molecular Structure , Quantum Theory
12.
J Magn Reson ; 144(2): 207-16, 2000 Jun.
Article in English | MEDLINE | ID: mdl-10828189

ABSTRACT

(13)C and (2)H spin-lattice relaxation times have been determined by inversion recovery in a range of site-specific (13)C- and (2)H-labeled saccharides under identical solution conditions, and the data were used to calculate deuterium nuclear quadrupolar coupling constants ((2)H NQCC) at specific sites within cyclic and acyclic forms in solution. (13)C T(1) values ranged from approximately 0.6 to 8.2 s, and (2)H T(1) values ranged from approximately 79 to 450 ms, depending on molecular structure (0.4 M sugar in 5 mM EDTA (disodium salt) in (2)H(2)O-depleted H(2)O, pH 4. 8, 30 degrees C). In addition to providing new information on (13)C and (2)H relaxation behavior of saccharides in solution, the resulting (2)H1 NQCC values reveal a dependency on anomeric configuration within aldopyranose rings, whereas (2)H NQCC values at other ring sites appear less sensitive to configuration at C1. In contrast, (2)H NQCC values at both anomeric and nonanomeric sites within aldofuranose rings appear to be influenced by anomeric configuration. These experimental observations were confirmed by density functional theory (DFT) calculations of (2)H NQCC values in model aldopyranosyl and aldofuranosyl rings.


Subject(s)
Magnetic Resonance Spectroscopy/methods , Monosaccharides/analysis , Deuterium/analysis , Isotopes , Models, Theoretical , Molecular Structure , Reproducibility of Results , Spin Labels
14.
J Appl Microbiol ; 85 Suppl 1: 45S-51S, 1998 Dec.
Article in English | MEDLINE | ID: mdl-21182692

ABSTRACT

Bacterial biofilms have been observed and reported on food and food-processing surfaces and can contribute to increased risks for product quality and food safety. The colonization of fruit and vegetables by pectynolitic bacteria like Pseudonomas fluorescens attributable to conditions such as soft rot, can also manifest as biofilms. A developed biofilm structure can provide a protective environment for pathogens such as Listeria monocytogenes reducing the effectiveness of sanitisers and other inhibitory agents. Understanding the colonization of bacteria on leaf surfaces is essential to the development of a better understanding of the leaf ecology of vegetable products. Studies of microbial colonization of leaf surfaces have been conducted using SEM and more recently using confocal microsocpy techniques. In the current study, a Leica TCS NT laser scanning confocal microscope was used to investigate biofilm formation using vital fluorescence staining on intact vegetable leaves. Reflection contrast and fluorescence three-dimensional imaging successfully delineated bacterial and biofilm morphology without disturbing the bacterial or leaf surface structure. The results demonstrate the presence and development of biofilm on the surface of lettuce. The biofilms appeared to originate on the cuticle in distinct micro-environments such as in the natural depression of the stomata, or in the intercellular junction. Bacteria also adhered to and developed biofilm colonies within an hour of contact and with clean stainless steel surfaces. Our study investigates the progression of biofilm formation from leaf colonization, and will assist in characterising the critical mechanisms of plant/host interaction and facilitate the development of improved preservation, sanitising and packaging strategies for minimally processed vegetable products.


Subject(s)
Bacterial Physiological Phenomena , Biofilms , Food Microbiology , Vegetables/microbiology , Bacteria/growth & development , Biofilms/growth & development , Food Handling/methods , Food Safety , Imaging, Three-Dimensional
15.
J Bone Joint Surg Br ; 79(4): 624-5, 1997 Jul.
Article in English | MEDLINE | ID: mdl-9250751

ABSTRACT

We compared the practice of four orthopaedic consultants as regards the use of MRI and arthroscopy to diagnose problems of the knee. In one year 324 arthroscopies and 66 MR scans were performed for this purpose. We found that MRI is a reliable and cheaper alternative to 'diagnostic arthroscopy'. We consider that patients with definite clinical signs merit an early 'therapeutic arthroscopy', but that all other knees should be investigated by MRI. This policy spares patients from unnecessary and expensive surgery. Arthroscopy for diagnostic purposes should be used only with a specific purpose. Modern MRI can and should replace "having a look".


Subject(s)
Arthroscopy , Knee Injuries/diagnosis , Magnetic Resonance Imaging , Adolescent , Adult , Aged , Aged, 80 and over , Arthroscopy/economics , Child , Female , Humans , Knee Injuries/economics , Magnetic Resonance Imaging/economics , Male , Middle Aged
16.
Ann R Coll Surg Engl ; 79(4): 296-8, 1997 Jul.
Article in English | MEDLINE | ID: mdl-9244077

ABSTRACT

While much has been written on surgical theatre design, little can be found on the design of theatre scrubrooms. An audit of theatres at a modern district general hospital (DGH) revealed that only one scrubroom had the minimum free floor space required and none complied with other baseline parameters. A survey of surgeons revealed that 60% had to re-scrub because their hands had desterilised through insufficient scrubroom space. The implications for hygiene hazards are clear. We review the literature and outline the basic dimensions which should be incorporated in the design of modern theatre scrubrooms.


Subject(s)
Hand Disinfection , Hospital Design and Construction/standards , Operating Rooms/standards , Attitude of Health Personnel , England , Hospitals, District , Hospitals, General , Humans , Medical Staff, Hospital/psychology
17.
Vet Rec ; 138(19): 468-71, 1996 May 11.
Article in English | MEDLINE | ID: mdl-8735539

ABSTRACT

Thirty-two pigs were infested experimentally with Sarcoptes scabiei var suis and allocated randomly to a medicated group (injected intramuscularly with 300 micrograms doramectin/kg) or an unmedicated group (injected intramuscularly with 1 ml saline/33 kg). They were observed daily for 15 minutes for signs of pruritus, and the ear lesions were assessed and skin scrapings examined for mites on days 7, 14, 21 and 28 after treatment. In the 16 pigs treated with doramectin the ear lesions resolved completely within 14 days, no mites were recorded on 15 of them on day 7 or on any of them on days 14, 21 and 28; pruritus was greatly reduced from day 7 onwards (range 0 to 0-62 rubbing episodes per pig per day) and papular skin lesions were absent from 15 of the pigs at slaughter on day 28. In comparison, the ear lesions in the 16 unmedicated pigs failed to resolve in 15 of them. Mites were present on 15 of them at different times during the experiment; the numbers of rubbing episodes ranged from 0.88 to 4.65 per pig per day and all the pigs had papular skin lesions at slaughter. In the unmedicated pigs, both the degree of pruritus and the presence and severity of papular skin lesions at slaughter were greater in those with zero or low mite counts than in those with high mite counts.


Subject(s)
Anthelmintics/administration & dosage , Hypersensitivity/veterinary , Ivermectin/analogs & derivatives , Scabies/veterinary , Swine Diseases/drug therapy , Animals , Female , Hypersensitivity/drug therapy , Hypersensitivity/parasitology , Hypersensitivity/pathology , Injections, Intramuscular/veterinary , Ivermectin/administration & dosage , Male , Scabies/drug therapy , Scabies/parasitology , Scabies/pathology , Swine , Swine Diseases/parasitology , Swine Diseases/pathology , Treatment Outcome
18.
J Wildl Dis ; 30(2): 257-9, 1994 Apr.
Article in English | MEDLINE | ID: mdl-8028112

ABSTRACT

Dermatitis associated with natural infestation of a yellow-footed rock wallaby (Petrogale xanthopus xanthopus) with larvae of the chigger mite, Odontacarus (Leogonius) adelaideae is described. This record extends the known host range of O. adelaideae and is the first from a native animal in southern Australia.


Subject(s)
Macropodidae/parasitology , Skin/pathology , Trombiculiasis/veterinary , Trombiculidae/pathogenicity , Animals , Larva/pathogenicity , Male , Skin/parasitology , Trombiculiasis/pathology
20.
Vet Rec ; 130(26): 572-4, 1992 Jun 27.
Article in English | MEDLINE | ID: mdl-1496769

ABSTRACT

Four trials including 11,266 sheep were conducted in South Africa to evaluate the efficacy of the systemic parasiticide ivermectin against field outbreaks of sheep scab (Psoroptes ovis) when two doses of approximately 200 micrograms/kg were administered subcutaneously seven days apart (days 0 and 7). As sheep scab is a notifiable disease in South Africa, it was not possible to include an untreated control group. The prevalence of clinically affected animals in the four treated flocks varied from 0.4 per cent to 99 per cent before the two treatments. After the treatments, there were no signs of active clinical infection in any of the sheep between days 28 and 30, or at subsequent examinations. P ovis mites were recovered from scrapings from 114 of 127 indicator sheep before the treatment but no mites were recovered from them between days 28 and 30 or 42 and 58 after the treatments.


Subject(s)
Disease Outbreaks/veterinary , Ivermectin/therapeutic use , Mite Infestations/veterinary , Sheep Diseases/drug therapy , Animals , Female , Male , Mite Infestations/drug therapy , Mite Infestations/epidemiology , Mites/isolation & purification , Sheep , Sheep Diseases/epidemiology , Skin/parasitology , South Africa/epidemiology
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