2-Hydroxypyridine-Ligated Pd-complexes as pre-catalysts in Hydrogen Borrowing Chemistry α -Alkylation of Ketones Using Alcohols

An efficient method for selective alpha-alkylation of ketones with alcohols was developed using 2-hydroxypyridine-based ligands coordinated by palladium as pre-catalysts. The reactions were performed without additional additives under mild reaction conditions. The method is environmentally friendly to build C-C bond as water is the only byproduct. This tandem reaction proceeds via dehydrogenation reaction, aldol condensation and hydrogenation processes using hydrogen borrowing from the alcohols. The pre-catalyst was characterized by NMR, IR and XRD. Time profile study investigated by NMR and GC.In certain parts of chemistry, it is important to be able to design organic molecules so that they have exactly same structure that you are looking for. C-C bond formation is very important reaction in synthesis of products such as pharmaceuticals, natural products, agrochemical and in the plastics industry. There are variety of organic reactions that can be used to couple and build molecules differently. Recently, there has been great interest in using alcohols as starting materials for C-C bond formation processes. As they are less toxic, cheap, environmentally friendly. Alcohols are readily available alkylating agents however they are unreactive as alkylating agents because hydroxy group cannot be easily replaced by nucleophilic reagents. The common ways to convert alcohols to carbonyl compounds is by using wide range of oxidizing agents in stoichiometric and over stoichiometric amount by using metal oxides or metal salts for oxidation. These procedures produce heavy metal waste that is not compatible with environmental regulations. Therefore, the search for environmentally friendly, selective, and efficient methods is a great challenge for chemists. Metal catalyzed dehydrogenation or oxidative dehydrogenation have been found an interesting alternative. Catalysis has become one of the cornerstones in organic synthesis, as it increases the rate of a chemical reaction, theoretically without being consumed itself. This occurs by lowering the activation energy compared to uncatalyzed reaction. Transition metal catalyzed cross coupling reaction between alcohols and ketones is attractive strategy for alpha alkylation of ketone. 2-Hydroxy pyridine ligands have been found to catalyze hydrogenation and dehydrogenation reactions. Therefore, the aim of the project is to prepare 2- hydroxy pyridine and quinoline ligands then coupled with palladium chloride to study hydrogenation and dehydrogenation reactions between alcohols and ketones. An advantage of this reaction is it follows borrowing hydrogen approach for α-alkylation of benzyl alcohol with acetophenone and produces water as only byproduct which is in accordance with green chemistry. The reaction is proceeding via hydrogen transfer strategy and alcohols are source of hydrogen. The reactions were performed without additional additives under mild reaction conditions using KOtBu, 1-Pd catalyst in toluene at 120oC for 48 hours under nitrogen in carousal. The reaction proceeds via dehydrogenation reaction, aldol condensation and hydrogenation processes using hydrogen borrowing approach

The Impact of Educational and Gender Inequality on Income Inequality in South Asia

This paper examines the impact of educational and gender inequality in education on income inequality in South Asian countries for the time period of 1980 to 2010. Random effect model (REM) and fixed effect model (FEM) are used for estimation. Using the concept of education Gini the study find that there exist a positive relationship between educational and income inequality. The results also indicate that gender inequality in education at primary and tertiary level has positive and significant impact on income inequality but gender inequality at secondary level has negative and significant impact on income inequality. On the other hand, gender inequality at primary and tertiary level of education has negative impact on per capita income, while at secondary level has positive impact. The results also confirm that there exist U shaped Kuznets curve for the relationship between average year of schooling and inequality in education

The Impact of Educational and Gender Inequality on Income Inequality in South Asia

This paper examines the impact of educational and gender inequality in education on income inequality in South Asian countries for the time period of 1980 to 2010. Random effect model (REM) and fixed effect model (FEM) are used for estimation. Using the concept of education Gini the study find that there exist a positive relationship between educational and income inequality. The results also indicate that gender inequality in education at primary and tertiary level has positive and significant impact on income inequality but gender inequality at secondary level has negative and significant impact on income inequality. On the other hand, gender inequality at primary and tertiary level of education has negative impact on per capita income, while at secondary level has positive impact. The results also confirm that there exist U shaped Kuznets curve for the relationship between average year of schooling and inequality in education

Perceptions of teachers on government school privatization in Punjab, Pakistan

The educational privatization is the global phenomenon with far-reaching implications, and its impact on teachers in government schools within the context of Punjab, Pakistan, is a subject of dominant importance. Research investigates the effects of privatization upon teachers' job security, salaries, and job satisfaction. Study includes a mixed-methods approach, combining survey data from 430 teachers with in-depth interviews of 25 teachers. The results reveal that educational privatization in Punjab presents uncertainties about teachers' job security and contractual terms, reduces their autonomy and creates financial stress. Thus, on the positive side, teachers experience improvements in resources and teaching environments. However, impact of privatization on the teachers' job satisfaction is complex, with a blend of positive & negative emotions. The study underlines the need for balanced approach in the privatization policies, recognizing the teachers' multifaceted experiences. The policymakers must ensure that teachers' well-being and economic stability are not compromised. Findings donate to understanding of the impact of privatization on teachers in a specific context and call for further research to explore long-term effects and the perspectives of other stakeholders

Childhood-Onset systemic lupus erythematosus: a cohort study

Objective: To determine the clinical and immunological characteristics and short-term outcome of children with systemic lupus erythematosus (SLE).Study Design: A descriptive cohort study.Place and Duration of Study: Paediatric Rheumatology Clinic, The Aga Khan University Hospital, Karachi, from January 2011 to December 2015.Methodology: Clinical and immunological profile and short-term outcome of children less than 16 years of age admitted in the paediatric ward, with the diagnosis of SLE was studied. Demographic data, clinical presentation, laboratory findings, immunological profile and treatment regimens of these children were evaluated.Results: Thirty-two children, satisfying the criteria of American College of Rheumatology (ACR) for SLE, were enrolled during the study period of five consecutive years. A female predominance was observed with 28 (87.5%) patients being female (F:M 7:1). Mean age at symptom onset was 10.5 +2.7 years; and 8.8 +2.1 years in females and males, respectively. The mean age at diagnosis was 11.3 +2.8 years in females and 9.4 +1.9 years in males. Prolonged fever was the most common non-specific symptom found in 27 (84%), followed by pallor in 13 (41%) patients. Twenty-two (69%) children were found to be anemic and 18 patients (56%) having signs of arthritis at presentation. Renal involvement was observed in 15 (47%) patients. The most common laboratory finding was anemia, found in 22 (69%) of cases. The most common immunological markers were serum anti-neutrophil antibodies (ANA), positive in 28 (88%) patients, followed by anti double-stranded DNA antibodies, raised in 26 (81%) of cases. Out of 32, 12 patients were lost to follow-up. Of the remaining 20 children who were followed for four years, ten (50%) went into remission.Conclusion: Childhood-onset SLE encompasses a wide variety of manifestations with a female preponderance. Fever, arthralgia and pallor are the most frequent clinical manifestations among the children. Hemolytic anemia (HA) is the most common laboratory abnormality, with ANA and anti ds-DNA antibodies positivity in the majority of padiatric patients

Groundwater Quality Determination for Drinking Purpose by Using Water Quality Index Technique: A Case Study of Gadap Town, Karachi, Pakistan

Present study is aimed at assessment of groundwater quality of Gadap Town for drinking purpose using water quality index (WQI) technique. Gadap is located in the outskirt of Karachi city and mainly influenced by the agriculture activities. Groundwater samples (n = 22) were collected mainly from boring wells and a few through tube wells from variable depths (100-600 feet). The analytical results of water reveal occurrence of very high TDS (range: 466-3810; mean: 1402) and hardness contents (range: 250-2800 mg/L). On the other hand, pH varies (range: 6.9-8.1; mean: 7.5) within WHO guidelines (6.5-8.5) with a few samples showing turbidity. About one third of total collected samples (n = 8) were analyzed for qualitative determination of microbial contamination which are found positive, except one sample, indicating the sewage mixing. Major chemistry of groundwater is also found disturbed in terms of high content of Na (mean: 219 mg/L), K (mean: 15 mg/L), Ca (mean: 144 mg/L) and Mg (mean: mg/L 137). Similarly, anions varied in the order of Cl > HCO3 > SO4 > NO3. Although some parameters show the bad quality of water but Water quality index (WQI) value (16.18) indicates that the groundwater quality is suitable for drinking purpose. It is inferred from the present study that water quality is partly polluted due to anthropogenic activities mainly by sewage infiltration

Reconnoitering Mycobacterium tuberculosis lipoproteins to design subunit vaccine by immunoinformatics approach

Background: Tuberculosis is an aerosol transmitted disease of human beings caused by Mycobacterium tuberculosis (Mtb). The only available vaccine for Mtb is Bacillus Calmette-Guérin (BCG). Currently no alternative or booster is available for BCG. The objective of this predictive approach was based on binding of MHC-I and MHC-II and B cell epitopes of Mtb for mouse host.Methods: Immunoinformatics approach was used to design subunit vaccine (SV) by joining 8 MHC-I bindings, 6 MHC-II bindings, and 8 B-Cell epitopes with AAV, GPGPG, and KK amino acid linkers, respectively. The efficacy of the SV was enhanced through Mtb protein Rv3763 (LpqH, PDB ID= 4ZJM) as an adjuvant at the N-terminal of SV. The in silico analyses evaluated the SV to predict allergenicity, antigenicity, and physico-chemical properties.Results: Predictions revealed that SV is non-allergic and highly antigenic. The physico-chemical analysis showed that the SV was stable and basic in nature. The three-dimensional structure of SV was stable with a high binding affinity against the mouse TLR2 receptor. In silico cloning suggested the effective transformation of SV into the eukaryotic expression vector.Conclusion: This study permits preclinical validation of the designed SV in mouse host to confirm its immunogenic potential and efficacy, which will help in controlling tuberculosis.Keywords: Immunoinformatics; Docking; Subunit vaccine; Lipoprotein; Tuberculosis

Model-based in silico analysis of the PI3K/Akt pathway: the elucidation of cross-talk between diabetes and breast cancer

Background A positive association between diabetes and breast cancer has been identified by various epidemiological and clinical studies. However, the possible molecular interactions between the two heterogeneous diseases have not been fully determined yet. There are several underlying mechanisms which may increase the risk of breast cancer in diabetic patients. Introduction In this study, we focused on the role of O-GlcNAc transferase (OGT) enzyme in the regulation of phosphatidylinositol-3 kinase (PI3K) pathway through activation/deactivation of Akt protein. The efficiency of insulin signaling in adipocytes is reduced as a result of OGT overexpression which further attenuates Akt signaling; as a result, the efficiency of insulin signaling is reduced by downregulation of insulin-responsive genes. On the other hand, increased expression of OGT results in Akt activation in breast cancer cells, leading to enhanced cell proliferation and inhibition of the apoptosis. However, the interplay amongst these signaling pathways is still under investigation. Methods In this study, we used Petri nets (PNs) to model and investigate the role of PI3K and OGT pathways, acting as key players in crosstalk between diabetes and breast cancer, resulting in progression of these chronic diseases. Moreover, in silico perturbation experiments were applied on the model to analyze the effects of anti-cancer agents (shRNA and BZX) and anti-diabetic drug (Metformin) on the system. Results Our PN model reflects the alterations in protein expression and behavior and the correlation between breast cancer and diabetes. The analysis proposed two combination therapies to combat breast cancer progression in diabetic patients including combination of OGTmRNA silencing and OGT inhibitor (BZX) as first combination and BZX and Metformin as the second. Conclusion The PN model verified that alterations in O-GlcNAc signaling affect both insulin resistance and breast cancer. Moreover, the combination therapy for breast cancer patients consisting of anti-diabetic drugs such as Metformin along with OGT inhibitors, for example BZX, can produce better treatment regimens