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1.
Chem Commun (Camb) ; 58(67): 9341-9344, 2022 Aug 18.
Article in English | MEDLINE | ID: mdl-35880477

ABSTRACT

3-Dimensional (3D) cyanide coordination polymers, typically known as Prussian blue Analogues (PBAs), have received great attention in catalysis due to their stability, easily tuned metal sites, and porosity. However, their high crystallinities and relatively low number of surface-active sites significantly hamper their intrinsic catalytic activities. Herein, we report the utilization of a 2-dimensional (2D) layered cobalt tetracyanonickelate, [Co-Ni], for the reduction of protons to H2. Relying on its exposed facets, layered morphology, and abundant surface-active sites, [Co-Ni] can efficiently convert water and sunlight to H2 in the presence of a ruthenium photosensitizer (Ru PS) with an optimal evolution rate of 30 029 ± 590 µmol g-1 h-1, greatly exceeding that of 3D Co-Fe PBA [Co-Fe] and Co-Co PBA [Co-Co]. Furthermore, [Co-Ni] retains its structural integrity throughout a 6 hour photocatalytic cycle, which is confirmed by XPS, PXRD, and Infrared analysis. This recent work reveals the excellent morphologic properties that promote [Co-Ni] as an attractive catalyst for the hydrogen evolution reaction (HER).


Subject(s)
Hydrogen , Ruthenium , Catalysis , Cobalt/chemistry , Hydrogen/chemistry , Protons
2.
Inorg Chem ; 61(9): 3931-3941, 2022 Mar 07.
Article in English | MEDLINE | ID: mdl-35200012

ABSTRACT

The elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups.  K0.1[Co(bpy)]2.9[Fe(CN)6]2 ([Cobpy-Fe]), K0.2[Co(phen)]2.8[Fe(CN)6]2 ([Cophen-Fe]), {[Co(bpy)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 ([Cobpy2-Fe]), and {[Co(phen)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 Cl0.11 ([Cophen2-Fe]) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K0.1Co2.9[Fe(CN)6]2 ([Co-Fe]). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe], while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s-1, respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10-2 s-1). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers.

3.
AIDS Res Ther ; 16(1): 27, 2019 09 14.
Article in English | MEDLINE | ID: mdl-31521170

ABSTRACT

BACKGROUND: A negative status following confirmatory Early Infant Diagnosis (EID) is the desired pediatric outcome of prevention of Mother to Child Transmission (PMTCT) programs. EID impacts epidemic control by confirming non-infected HIV-exposed infants (HEIs) and prompting timely initiation of ART in HIV-infected babies which improves treatment outcomes. OBJECTIVES: We explored factors associated with EID outcomes among HEI in North-Central Nigeria. METHOD: This is a cross-sectional study using EID data of PMTCT-enrollees matched with results of HEI's dried blood samples (DBS), processed for DNA-PCR from January 2015 through July 2017. Statistical analyses were done using SPSS version 20.0 to generate frequencies and examine associations, including binomial logistic regression with p < 0.05 being statistically significant. RESULTS: Of 14,448 HEI in this analysis, 51.8% were female and 95% (n = 12,801) were breastfed. The median age of the infants at sample collection was 8 weeks (IQR 6-20), compared to HEI tested after 20 weeks of age, those tested earlier had significantly greater odds of a negative HIV result (≤ 6 weeks: OR = 3.8; 6-8 weeks: OR = 2.1; 8-20 weeks: OR = 1.5) with evidence of a significant linear trend (p < 0.001). Similarly, HEI whose mothers received combination antiretroviral therapy (cART) before (OR = 11.8) or during the index pregnancy (OR = 8.4) had significantly higher odds as compared to those whose mothers did not receive cART. In addition, HEI not breastfed had greater odds of negative HIV result as compared to those breastfed (OR = 1.9). CONCLUSIONS: cART prior to and during pregnancy, earlier age of HEI at EID testing and alternative feeding other than breastfeeding were associated with an increased likelihood of being HIV-negative on EID. Therefore, strategies to scale-up PMTCT services are needed to mitigate the burden of HIV among children.


Subject(s)
Early Diagnosis , HIV Infections/prevention & control , Infectious Disease Transmission, Vertical/prevention & control , Molecular Diagnostic Techniques/statistics & numerical data , Pregnancy Complications, Infectious/prevention & control , Anti-Retroviral Agents/therapeutic use , Cross-Sectional Studies , Dried Blood Spot Testing , Female , Humans , Infant , Infant, Newborn , Male , Mothers , Nigeria , Pregnancy , Pregnancy Complications, Infectious/virology , Retrospective Studies
4.
Neural Comput Appl ; 29(7): 317-328, 2018.
Article in English | MEDLINE | ID: mdl-29576689

ABSTRACT

The effective modelling of high-dimensional data with hundreds to thousands of features remains a challenging task in the field of machine learning. This process is a manually intensive task and requires skilled data scientists to apply exploratory data analysis techniques and statistical methods in pre-processing datasets for meaningful analysis with machine learning methods. However, the massive growth of data has brought about the need for fully automated data analysis methods. One of the key challenges is the accurate selection of a set of relevant features, which can be buried in high-dimensional data along with irrelevant noisy features, by choosing a subset of the complete set of input features that predicts the output with higher accuracy comparable to the performance of the complete input set. Kohonen's self-organising neural network map has been utilised in various ways for this task, such as with the weighted self-organising map (WSOM) approach and this method is reviewed for its efficacy. The study demonstrates that the WSOM approach can result in different results on different runs on a given dataset due to the inappropriate use of the steepest descent optimisation method to minimise the weighted SOM's cost function. An alternative feature weighting approach based on analysis of the SOM after training is presented; the proposed approach allows the SOM to converge before analysing the input relevance, unlike the WSOM that aims to apply weighting to the inputs during the training which distorts the SOM's cost function, resulting in multiple local minimums meaning the SOM does not consistently converge to the same state. We demonstrate the superiority of the proposed method over the WSOM and a standard SOM in feature selection with improved clustering analysis.

5.
Trans R Soc Trop Med Hyg ; 107(10): 627-30, 2013 Oct.
Article in English | MEDLINE | ID: mdl-23959003

ABSTRACT

BACKGROUND: Hepatitis A is an infectious viral disease, caused by hepatitis A virus (HAV), endemic in many developing countries. A recent review of the global prevalence of HAV infection and susceptibility by the WHO had few data on the seroprevalence of HAV in Nigeria. This study was designed to determine the seroprevalence of HAV among schoolchildren and adolescents in Kaduna State and to identify factors associated with seropositivity. METHODS: Questionnaires were administered to 403 participants aged 2-19 years, and blood samples were collected during April-July 2009 and screened for anti-HAV IgG using an anti-HAV IgG enzyme immunoassay kit. χ(2) and Fisher's exact tests were used to identify variables associated with the presence of anti-HAV IgG. RESULTS: The mean ± SD age of the study population was 11.7 ± 3.2 years. Of the 403 serum samples, 29 were positive for HAV, giving an overall seroprevalence of 7.2% (95% CI 4.9-10.2%) among the study population. Seropositivity with respect to age ranged from 4.6% (10/218; 95% CI 2.2-8.3%) in the 11-15 years age group to 30% (3/10; 95% CI 6.7-65.3%) in the ≤5 years age group. Anti-HAV seropositivity was associated with sewage disposal methods and parents' educational level (p < 0.05). CONCLUSION: This study shows that the majority of the study population lacked natural immunity (anti-HAV IgG). This low HAV exposure may be attributed to improvements in sanitary conditions and socioeconomic status. Further research involving an older population in different parts of the country is required to determine the current epidemiological pattern of HAV.


Subject(s)
Antibodies, Viral/blood , Hepatitis A virus/immunology , Hepatitis A/epidemiology , Adolescent , Child , Child, Preschool , Cross-Sectional Studies , Female , Hand Disinfection/methods , Hand Disinfection/standards , Hepatitis A/immunology , Hepatitis A/virology , Humans , Male , Nigeria/epidemiology , Sanitation/standards , Seroepidemiologic Studies , Surveys and Questionnaires , Water Supply/standards , Young Adult
6.
Pan Afr Med J ; 12: 108, 2012.
Article in English | MEDLINE | ID: mdl-23133708

ABSTRACT

BACKGROUND: Rotavirus (RV) is the most common cause of severe diarrhea in children <5 years of age worldwide accounting for 527,000 deaths annually. Over 80% of these deaths occur in South Asia and sub-Saharan Africa. RV vaccines have significantly reduced RV-associated morbidity and mortalities in several countries like the United States and Mexico while vaccine trials have proved efficacious in Ghana and other developing countries. However, there is paucity of data on RV infection in Cameroon where diarrhea is a major childhood disease. METHODS: A total of 534 stool specimens collected between January 2003 and December 2004 from children with acute gastroenteritis in five health districts in the NWR of Cameroon were screened for group A human rotavirus antigen by ELISA and their electropherotypes determined by Polyacrylamide gel electrophoresis. RESULTS: RV was detected in 153 (28.7%) diarrheic specimens with infection occurring throughout the year, being more common in children under two years of age (P < 0.01) with the highest incidence in the 7-9 months age group (P <0.05). Sub clinical infections (9%) occurred mostly in children aged 0 - 6 months old (P<0.01). Source of drinking water was not associated with RV infection. Eleven electropherotype patterns were detected with predominance of long electropherotypes (92.8%) and mixed electropherotypes were seen only in hospitalized children. Some isolates showed overlapping or merged genome segments 7 and 8 or 9 and presenting with 10 segments of the RV genome. CONCLUSION: RV is a significant cause of pediatric diarrhea in the NWR affecting mostly children under 2 years of age. Continuous RV surveillance and nationwide surveys are recommended to improve the health of young children in Cameroon. More research is needed to fully characterize the isolated RV strains.


Subject(s)
Diarrhea/epidemiology , Molecular Epidemiology , Rotavirus Infections/epidemiology , Rotavirus/isolation & purification , Age Distribution , Antigens, Viral/immunology , Cameroon/epidemiology , Child, Preschool , Diarrhea/virology , Electrophoresis, Polyacrylamide Gel , Enzyme-Linked Immunosorbent Assay , Female , Humans , Infant , Infant, Newborn , Male , Rotavirus Infections/mortality , Rotavirus Infections/virology
7.
PLoS One ; 6(3): e17865, 2011 Mar 14.
Article in English | MEDLINE | ID: mdl-21423811

ABSTRACT

HIV-1 CRF02_AG and subtype G (HIV-1G) account for most HIV infections in Nigeria, but their evolutionary trends have not been well documented. To better elucidate the dynamics of the epidemic in Nigeria we characterised the gag and env genes of North-Central Nigerian HIV-1 isolates from pregnant women. Of 28 samples sequenced in both genes, the predominant clades were CRF02_AG (39%) and HIV-1G (32%). Higher predicted proportion of CXCR4-tropic (X4) HIV-1G isolates was noted compared to CRF02_AG (p = 0.007, Fisher's exact test). Phylogenetic and Bayesian analysis conducted on our sequences and all the dated available Nigerian sequences on the Los Alamos data base showed that CRF02_AG and HIV-1G entered into Nigeria through multiple entries, with presence of HIV-1G dating back to early 1980s. This study underlines the genetic complexity of the HIV-1 epidemic in Nigeria, possible subtype-specific differences in co-receptor usage, and the evolutionary trends of the predominant HIV-1 strains in Nigeria, which may have implications for the design of biomedical interventions and better understanding of the epidemic.


Subject(s)
Evolution, Molecular , HIV-1/classification , HIV-1/genetics , Receptors, HIV/metabolism , Adolescent , Adult , Amino Acid Sequence , Anti-Retroviral Agents/therapeutic use , Bayes Theorem , Demography , Female , Genetic Variation , HIV Infections/drug therapy , HIV-1/isolation & purification , Humans , Models, Genetic , Molecular Sequence Data , Nigeria , Phylogeny , Pregnancy , Receptors, CXCR4/metabolism , Young Adult , env Gene Products, Human Immunodeficiency Virus/chemistry , env Gene Products, Human Immunodeficiency Virus/genetics , gag Gene Products, Human Immunodeficiency Virus/genetics
8.
J Wildl Dis ; 46(1): 267-71, 2010 Jan.
Article in English | MEDLINE | ID: mdl-20090042

ABSTRACT

During lyssavirus surveillance, 350 brains from four species of fruit bats and one species of insectivorous bat were collected from seven locations in Northern Nigeria during May to October, 2006. Lyssavirus antigen was not detected in the brains, and isolation attempts in mice were unsuccessful. However, serologic tests demonstrated the presence of lyssavirus-neutralizing antibodies in bat sera. Of 140 sera tested, 27 (19%) neutralized Lagos bat virus, and two of these additionally neutralized Mokola virus. The positive samples originated from the straw-colored fruit bat (Eidolon helvum) and the Gambian epaulet bat (Epomophorus gambianus). No neutralizing activity was detected against other lyssaviruses including rabies, Duvenhage, and West Caucasian bat viruses.


Subject(s)
Antibodies, Viral/blood , Chiroptera/virology , Lyssavirus/immunology , Rhabdoviridae Infections/veterinary , Sentinel Surveillance/veterinary , Animals , Disease Reservoirs/veterinary , Disease Reservoirs/virology , Lyssavirus/isolation & purification , Nigeria/epidemiology , Rhabdoviridae Infections/epidemiology , Seroepidemiologic Studies , Serologic Tests/veterinary
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