Raman spectroscopy insights into the α- and δ-phases of formamidinium lead iodide (FAPbI3).

Solar perovskites have received phenomenal attention and success over the past decade, due to their high power conversion efficiencies (PCE), ease of fabrication and low cost which has enabled the prospect of them being a real commercial contender to the traditional silicon technology. In one of the several developments on the archetypal MAPbI3 perovskite absorber layer, FAPbI3 was found to obtain a higher PCE, likely due to its more optimum band gap, with doping strategies focusing on the inclusion of MA+/Cs+ cations to avoid the unfavourable phase transformation to a photoinactive phase. To better understand the phase change from the photoactive cubic (Pm3[combining macron]m) black (α) phase to the unwanted photoinactive (P63/mmc) yellow (δ) phase, we make use of variable temperature Raman spectroscopy to probe the molecular species and its relationship to the inorganic framework. We show for the first time there to be no Raman active modes for the α phase up to 4000 cm-1, which can be correlated to the Pm3[combining macron]m cubic symmetry of that phase. Our detailed studies suggest that previous reports of the observation of Raman peaks for this phase are likely associated with degradation reactions from the localised laser exposure and the formation of Raman active lead oxide. In addition, we have identified water as a contributing factor to the transformation, and observed a corresponding signal in the Raman spectra, although confirmation of its exact role still remains inconclusive.

Short communication: Correlation between within-herd antibody-prevalence and bulk tank milk antibody levels to Mycobacterium avium ssp. paratuberculosis using 2 commercial immunoassays.

The objective of this study was to determine the correlation between the results obtained with the ELISA technique for antibodies to Mycobacterium avium ssp. paratuberculosis in serum and bulk tank milk at the herd level. For this purpose, 203 samples of bulk tank milk were analyzed with 2 commercial ELISA from dairy herds with a prevalence of seropositive animals that was also determined. In regard to the reference test (results in blood serum), the sensitivity of the bulk tank milk test to detect high-positive herds (≥10% seroprevalence) ranged from 85.7 to 71.4%. The specificity to detect herds with no seropositive animals ranged from 70.5 to 53%. In a quantitative approach, Pearson correlation coefficients, reported as a measure of the linear association between herd seroprevalences and transformed optical density values recorded in bulk tank milk, were 0.39 and 0.54 for the studied ELISA. Although the test results were relatively fairly correlated with the within-herd prevalence, the practical utility of bulk tank milk testing for Mycobacterium avium ssp. paratuberculosis seems limited, especially regarding specificity.

Study on some risk factors and effects of bovine ketosis on dairy cows from the Galicia region (Spain).

The study was designed to determine the relation between ß-hydroxybutyrate (BHB) concentrations in milk from dairy cows after calving and the length of the previous lactation, the dry period and the 305-day normalized production, and to assess the influence of BHB concentrations on culling and test-day milk productions and somatic cell counts (SCC) throughout the lactation that followed the BHB measurement. The data used in the study were obtained from 59 187 cows in the Galicia region (Spain). BHB determination was performed using Fourier-transformed infrared spectrometry from the milk samples collected from each cow on the first post-partum test day. For statistical analysis, the following methods were applied: (i) ordinal regression to assess the effect of the length of the previous lactation, the dry period and the 305-day normalized milk production on milk BHB, (ii) a Cox model to estimate the influence of the BHB concentration on risk of culling (overall and for a variety of reasons) and (iii) linear regression to assess the link between BHB and the milk yield and SCC obtained from each of the tests day performed throughout lactation. The probability of having higher BHB concentrations increased when the length of the previous lactation (p = 0.006), the dry period (p = 0.003) and the 305-day normalized milk yield (p = 0.005) increased. However, the slight increase observed (especially for the case of the dry period and the 305-day milk yield) would not justify that measures be implemented to reduce these traits. Higher concentrations of BHB led to an increased risk of culling due to 'death' (p ≤ 0.001) and 'urgent slaughter' (p ≤ 0.002) (both causes of involuntary culling). It also led to a reduction in milk production (p < 0.001) and an increase in SCC (p < 0.001) in the post-partum; from that moment onward (including peak lactation), there were no differences in those two parameters depending on the BHB levels.

Genetic diversity of bovine viral diarrhea viruses from the Galicia region of Spain.

This study examined the frequency and diversity of bovine viral diarrhoea viruses (BVDVs) infecting cattle in Galicia (northwestern Spain). A total of 86 BVDV strains were typed in samples of serum from 79 persistently infected animals and 3 viraemic animals and of abomasal fluid from 4 fetuses. Samples came from 73 farms participating in a voluntary BVDV control programme. Typing was based on a 288-bp sequence from the 5' untranslated region amplified using primers 324 and 326. Of the 86 strains, 85 (98.8 per cent) belonged to species BVDV-1 and 1 (1.2 per cent) belonged to BVDV-2; 73 strains (84.9 per cent) were typed as BVDV-1b, 2 as BVDV-1e and 6 as BVDV-1d. One strain each was typed as belonging to 1a, 1h, 1k and 1l. The sole BVDV-2 strain was classified as 2a. These results identify BVDV-1b as the predominant species, and they indicate the presence of viral types not previously described anywhere in Spain. This is also the first report of BVDV-2 in Galicia and only the second report of BVDV-2 in Spain.

Bovine herpesvirus 1: within-herd seroprevalence and antibody levels in bulk-tank milk.

The aim of the present study was to establish a relationship between the results obtained with the enzyme-linked immunosorbent assay (ELISA) technique for antibodies (against bovine herpesvirus 1) in serum and those in milk at the herd level. For this purpose, 275 samples of bulk-tank milk were analysed with glycoprotein E (gE) antibody ELISA and 207 more were analysed with glycoprotein B (gB) antibody ELISA (482 in total). All of these samples came from dairy herds whose seroprevalence was also evaluated. The results of this study were then used to analyse the sensitivity of the bulk-tankmilk test in detecting herds with a high risk of active infection (>60% seroprevalence) and its specificity in detecting those with few (<20%) or no seropositive animals. In regard to the reference test (results in blood serum), the sensitivity of the bulk-tankmilk test in detecting herds with >60% seropositive animals was 100% for both gE and gB ELISAs. The specificity figures, for gE and gB ELISAs, respectively, were 88.4% and 99.1% for infection-free herds and 72.6% and 96% for herds with <20% seroprevalence. In a quantitative approach, Pearson's correlation coefficients, reported as a measure of linear association between herd seroprevalences and transformed optical density values recorded in bulk-tank milk, were -0.63 for gE ELISA and 0.67 for gB ELISA.

Les auteurs présentent une étude visant à faire ressortir la corrélation entre les résultats obtenus à l'échelle du troupeau au moyen d'une épreuve immunoenzymatique (ELISA) pour la détection d'anticorps dirigés contre l'herpèsvirus bovin de type 1 dans des échantillons de sérum et ceux obtenus dans le lait. À cet effet, 275 échantillons de lait de citerne ont été soumis à un test ELISA visant à déceler la présence d'anticorps dirigés contre la glycoprotéine E (gE) du virus, et 207 autres ont été analysés au moyen d'un test ELISA visant à déceler la présence d'anticorps dirigés contre la glycoprotéine B (gB) (482 échantillons analysés au total). La totalité des échantillons provenait d'élevages laitiers dans lesquels la séroprévalence a également été evaluée. Les résultats de l'étude ont ensuite permis d'analyser la sensibilité du test sur le lait de citerne, c'est-àdire la capacité de ce test à détecter les troupeaux présentant un risque élevé d'infection active (séroprévalence > 60 %), ainsi que sa spécificité, c'est-à-dire sa capacité à détecter les troupeaux dans lesquels le pourcentage d'animaux séropositifs était faible (moins de 20 %) ou nul (0 %). Comparativement au test de référence (analyse des échantillons de sérum), la sensibilité des tests ELISA sur le lait de citerne était de 100 % (détection de tous les troupeaux dotés d'au moins 60 % d'animaux possédant des anticorps dirigés contre la glycoprotéine E ou B). En termes de spécificité des tests ELISA anti-gE et anti-gB, les valeurs étaient, respectivement, de 88,4 % et 99,1 % dans les troupeaux indemnes et de 72,6 % et 96 % dans les troupeaux accusant une séroprévalence inférieure à 20 %. Les coefficients de corrélation de Pearson obtenus par une méthode quantitative pour exprimer la relation linéaire entre les prévalences sérologiques et les valeurs de densité optique modifiées dans le lait de citerne étaient respectivement de ­0,63 pour l'ELISA gE et de 0,67 pour l'ELISA gB.

Los autores describen un estudio encaminado a determinar si existe una relación, y de ser así cuál, entre los resultados del ensayo inmunoenzimático (ELISA) de detección de anticuerpos (contra el herpesvirus bovino 1) en suero y los resultados obtenidos al analizar la leche de rebaños enteros. Para ello se sometieron 275 muestras de leche de tanque a la prueba ELISA de detección de anticuerpos contra la glicoproteína E (gE) y otras 207 muestras a la prueba ELISA de detección de anticuerpos contra la glicoproteína B (gB) (esto es, un total de 482 muestras). Todas esas muestras procedían de rebaños lecheros cuya prevalencia serológica también se calculó. A partir de los resultados del estudio se determinó la sensibilidad de la prueba practicada en la leche de tanque para detectar rebaños con un elevado riesgo de infección activa (más del 60% de animales seropositivos) y su especificidad para detectar aquellos rebaños con pocos (menos del 20%) animales seropositivos o ninguno (0%). En comparación con la prueba de referencia (resultados del análisis sérico), la sensibilidad del análisis de la leche de tanque para detectar rebaños con más de un 60% de animales seropositivos fue del 100% en el caso de ambas pruebas ELISA (gE y gB). En cuanto a la especificidad, las técnicas ELISA para la gE y la gB permitieron detectar respectivamente un 88,4% y un 99,1% de los rebaños libres de infección y un 72,6% y un 96% de los rebaños con menos de un 20% de animales seropositivos. El análisis cuantitativo de los resultados deparó coeficientes de correlación de Pearson, utilizados como medida de la relación lineal entre las seroprevalencias de rebaño y los valores transformados de densidad óptica obtenidos en la leche de tanque, de ­0,63 para el ELISA gE y de 0,67 para el ELISA gB.

Monitoring the bulk milk antibody response to bovine viral diarrhea in dairy herds vaccinated with inactivated vaccines.

This study was designed to determine long-term responses in dairy herds after vaccination with 1 of 3 inactivated bovine viral diarrhea virus (BVDV) vaccines with regard to antibodies against p80 protein in bulk tank milk samples, as detected by ELISA. In the present study, 29 dairy herds were vaccinated with Bovilis BVD (MSD Animal Health, Milton Keynes, UK), 11 with Hiprabovis Balance (Laboratorios Hipra, Amer, Spain), and 9 with Pregsure BVD (Zoetis, Florham Park, NJ). In these herds, bulk tank milk samples were collected and examined at the time of the first vaccination and every 6 mo during a 3-yr period. Samples were analyzed with a commercial ELISA test for the p80 protein of BVDV. The results demonstrated that vaccination affected the level of antibodies against p80. Hence, vaccination status should be taken into consideration when interpreting bulk tank milk antibody tests.

Order/disorder phenomena in Zn1-xMnxGa2Se4 ordered vacancy compounds: high temperature neutron powder diffraction experiments.

We present a study of order-disorder phenomena in the series of tetrahedral ordered vacancy compounds Zn1-xMnxGa2Se4 by means of time-of-flight neutron diffraction at high temperature together with dc magnetic susceptibility, Raman spectroscopy, differential thermal analysis and optical absorption experiments. Samples of nominal composition x = 0, 0.24, 0.5, 0.77 and 1 have been studied. An order-disorder phase transition has been detected, with Tc ranging from 472 to 610 ° C, which involves a structural change from a defect chalcopyrite phase, with I4 space group (s.g.) and three different cation sites, to a partially disordered defect stannite, in which Zn, Mn and half of the Ga ions share the 4d site in I42m s.g. Neither the vacancies nor the Ga ions occupying site 2a are involved in the phase transition. An additional ordering process is observed on approaching the phase transition from below, which is attributed to several factors: the activation of cation diffusion at ∼300 ° C, the partially disordered cation distribution exhibited by the as-grown single crystals and the preference of Mn atoms for the 2d crystallographic site in the I4 structure. The reversibility of the phase transition is analysed with the aid of magnetic, optical and Raman experiments.

Thermally activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations.

Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I4¯2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I4¯ space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4.

The use of crossbreeding with beef bulls in dairy herds: effects on calving difficulty and gestation length.

This study was designed to analyse the evolution in the use of beef bull semen for dairy cattle insemination and, mainly, to assess calving difficulty, gestation length and proportion of stillbirths after breeding pure Holsteins or crossbreeding. Data were collected during 2004 to 2011 for 552 571 Holstein calvings (457 070 Holstein × Holstein, 43 384 Holstein × Limousine, 32 174 Holstein × Belgian Blue and 19 943 Holstein × Galician Blonde). The highest calving difficulty, compared with pure Holsteins was for crosses with Belgian Blue followed by Limousine and Galician Blonde. The Holstein × Limousine and Holstein × Galician Blonde crossbred calves had significantly longer gestation lengths than Holstein × Holstein and Holstein × Belgian Blue calves. Between the latter two, pure Holstein had the shortest gestation length. Calving difficulty and gestation length decreased as the age of the dam advanced. The most difficult calvings were observed in twin calvings, followed by the calvings of male calves and female calves. The gestations leading to the birth of male calves were longer than those leading to female calves and twin calves. Stillbirths were not related to the breed used for mating. Through examining these parameters, sire breed should be considered when selecting a beef breed for the insemination of milk-producing dams.

Apatite germanates doped with tungsten: synthesis, structure, and conductivity.

High oxygen content apatite germanates, La(10)Ge(6-x)W(x)O(27+x), have been prepared by doping on the Ge site with W. In addition to increasing the oxygen content, this doping strategy is shown to result in stabilisation of the hexagonal lattice, and yield high conductivities. Structural studies of La(10)Ge(5.5)W(0.5)O(27.5) show that the interstitial oxygen sites are associated to a different degree with the Ge/WO(4) tetrahedra, leading to five coordinate Ge/W and significant disorder for the oxygen sites associated with these units. Raman spectroscopy studies suggest that in the case of the WO(5) units, the interstitial oxygen is more tightly bonded and therefore not as mobile as in the case of the GeO(5) units, thus not contributing significantly to the conduction process.

Effect of the sampling device on fat and protein variation in cow milk samples obtained for official milk recording.

The paper was designed to assess the effect of the type of milk meter used by dairy farms for official milk testing to obtain individual milk samples for fat and protein determination. This study was performed in 2006 in Galicia, which is Spain's main dairy cattle region; data were collected from 2,149 Holstein cow farms enrolled for official milk recording. Findings indicate that the milk sampling system used has a substantial effect on the fat contents recorded for individual milk samples. Such variation could arise from poor functioning of the equipment, inadequate mixing of the milk portion from which the sample is obtained, or from the nonproportionality of the sample. Samples obtained from only one point in the milk line may not be representative of all the milk produced. The most significant differences are observed in the percentage of fat, whereas differences in percentage of protein are smaller. The sampling method used should, but does not always, provide a representative sample of the milk from a single milking.

Application of ATP bioluminescence for evaluation of surface cleanliness of milking equipment.

The ATP bioluminescence method was used to evaluate the cleanliness of milking equipment surfaces (teat cup rubbers, teat dip containers, milk receivers, and pipeline joints) in dairy farms in Galicia (northwest Spain) with parlour, pipeline tie-stall or bucket tie-stall milking systems. The cleanest surfaces were teat cup rubbers. The use of non-chlorinated water for cleaning, and of pipeline or bucket tie-stall milking systems, was associated with high ATP bioluminescence values. However, ATP bioluminescence values only explained 12% of the variability in bulk-tank bacterial count; this is attributable to the importance of other factors (notably the correct functioning of the tank cooling system) for maintenance of low bacterial count.

Management practices associated with Mycobacterium avium subspecies paratuberculosis infection and the effects of the infection on dairy herds.

During 2004, a survey of Mycobacterium avium subspecies paratuberculosis (map) was conducted in 101 randomly selected dairy herds to investigate associations between the infection status of the herds, different management practices, and possible disease indicators, such as indices of mastitis and reproductive performance. Data were collected by means of a questionnaire through personal interviews with the farmers and veterinarians in charge of each farm. At the same time, blood samples were taken from cattle over one year old and analysed with a commercial elisa to detect antibodies to map. Statistical analyses indicated that the following management practices constituted major risk factors: utilisation of colostrum from cows with a previous positive map diagnosis, and housing replacement calves with adult cattle before they were six months old. Seropositivity to map was related to the herds' bulk tank somatic cell counts and incidence of clinical mastitis, but not to their reproductive performance.

Prevalence of and risk factors for Listeria species on dairy farms.

This cross-sectional study determined the prevalence of Listeria spp. in bulk-tank milk on dairy farms in the region of Galicia in northwest Spain. The aim was to identify management practices associated with the presence of Listeria spp. and possible effects on milk hygienic quality. A total of 98 farms was randomly selected on the basis of an expected prevalence of 6.5% for Listeria monocytogenes from 20,107 dairy farms in the region. Bulk-tank milk samples were obtained from 98 farms, fecal samples from lactating cows from 97 farms, and silage samples from 83 farms. Listeria monocytogenes was detected in 6.1, 9.3, and 6.0% of these samples, respectively. Statistical analyses confirmed the relationship between low silage quality (as indicated by high pH) and presence of Listeria spp. in silage (29.5 vs. 6.2% for pH above or below 4.5, respectively). Only milking system [tie-stall systems (28.6%) vs. parlor milking (10%)] and inadequately controlled milking order [yes (32.0%) vs. no (10.7%)] had statistically significant effects on management practices for increasing the risk of Listeria contamination of bulk-tank milk.

Raman spectroscopic study of cation disorder in poly- and single crystals of the nickel aluminate spinel.

The Raman spectrum of NiAl(2)O(4) inverse spinel has been studied in quenched polycrystalline pellets produced by solid-state reaction and in single crystals grown by the floating zone method. The lattice parameters and inversion degrees were determined by x-ray diffraction. Polarization measurements in single crystals allow mode symmetry assignment. Then, a correlation is established between the bands observed in polycrystalline samples and those of single crystals. Both kinds of sample present more bands than the five expected (A(1g)+E(g)+3T(2g)) in a cubic Fd3m spinel. This multiplicity is attributed to the almost fully inverted cation distribution in NiAl(2)O(4), with inversion parameter x≈0.9. The multiplicity of the high-frequency A(1g) band, in particular, is attributed to the different possible configurations of Ni(2+) and Al(3+) cations occupying the three octahedral sites close to a given oxygen ion. A strong downshift of the E(g) mode frequency, as compared to the normal spinel MgAl(2)O(4), is attributed to the longer bonding distance between oxygen and octahedral cations in inverse II-III spinels. Due to the small range of variation of x upon thermal treatment in NiAl(2)O(4), no significant differences were found between the spectra of samples quenched at different temperatures, from 800 to 1200 °C.

Serological study of the frequency of leptospiral infections among dairy cows in farms with suboptimal reproductive efficiency in Galicia, Spain.

Between March 1996 and September 1997, 15 farms located in Galicia (NW Spain) and experiencing suboptimal reproductive efficiency were visited and blood samples were obtained from all the lactating cows (n=442). Additionally, 1060 samples were obtained monthly from a cohort of 219 lactating cows belonging to nine of the farms between March 1996 and April 1997. All the samples were tested by microscopic agglutination (MAT) using live antigens representing the following Leptospira interrogans serogroups: Australis, Autumnalis, Ballum, Canicola, Grippotyphosa, Icterohaemorrhagiae, Louisiana, Pomona, Sejroe, Shermani and Tarassovi. Eighty-one of the 442 cows were positive against one or more serogroups (P=18.33%). Serologically, L. bratislava and L. grippotyphosa were detected as the most prevalent serovars (P=7.92 and 7.69%, respectively) and as the serovars against which the probability of seroconversion was highest (P=0.27 and 0.25, for a 12-month period, respectively) among those studied. The proportional hazards regression method was used for evaluating the seasonal trend of seroconversions against these two serovars. The risk of seroconversion against L. grippotyphosa was significantly higher during spring. The risk of seroconversion against L. bratislava did not differ significantly among seasons. Our results suggest that infections by L. bratislava did not follow, among the study animals and during the study period, the pattern typically described for non-adapted serovars, pointing out the possibility that some strains of this serovar could behave as adapted serovars.

Influenza A viruses: epidemiologic study in fatteners in Spain (1987-89).

2,979 sera were collected from slaughtered swine in two geographic areas of Spain from 1987 to 1989. They were tested for antibodies against an H1N1- and H3N2-influenza virus by haemagglutination-inhibition tests (HI). The percentage of positive sera was higher in area I (78%-69.2%) than in area II (63.1%-60.4%) for both viruses respectively. The coexistence of high titres to both H1N1- and H3N2-influenza virus became apparent in cold months simultaneously in each area, although influenza viruses circulated in the Spanish swine population for two years. Also this study suggests the possible circulation of A/Texas/1/77-like strains in Spain, results which have not been reported before.