Search results for: Seema Saini
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 101

Search results for: Seema Saini

11 Performance Analysis of Double Gate FinFET at Sub-10NM Node

Authors: Suruchi Saini, Hitender Kumar Tyagi

Abstract:

With the rapid progress of the nanotechnology industry, it is becoming increasingly important to have compact semiconductor devices to function and offer the best results at various technology nodes. While performing the scaling of the device, several short-channel effects occur. To minimize these scaling limitations, some device architectures have been developed in the semiconductor industry. FinFET is one of the most promising structures. Also, the double-gate 2D Fin field effect transistor has the benefit of suppressing short channel effects (SCE) and functioning well for less than 14 nm technology nodes. In the present research, the MuGFET simulation tool is used to analyze and explain the electrical behaviour of a double-gate 2D Fin field effect transistor. The drift-diffusion and Poisson equations are solved self-consistently. Various models, such as Fermi-Dirac distribution, bandgap narrowing, carrier scattering, and concentration-dependent mobility models, are used for device simulation. The transfer and output characteristics of the double-gate 2D Fin field effect transistor are determined at 10 nm technology node. The performance parameters are extracted in terms of threshold voltage, trans-conductance, leakage current and current on-off ratio. In this paper, the device performance is analyzed at different structure parameters. The utilization of the Id-Vg curve is a robust technique that holds significant importance in the modeling of transistors, circuit design, optimization of performance, and quality control in electronic devices and integrated circuits for comprehending field-effect transistors. The FinFET structure is optimized to increase the current on-off ratio and transconductance. Through this analysis, the impact of different channel widths, source and drain lengths on the Id-Vg and transconductance is examined. Device performance was affected by the difficulty of maintaining effective gate control over the channel at decreasing feature sizes. For every set of simulations, the device's features are simulated at two different drain voltages, 50 mV and 0.7 V. In low-power and precision applications, the off-state current is a significant factor to consider. Therefore, it is crucial to minimize the off-state current to maximize circuit performance and efficiency. The findings demonstrate that the performance of the current on-off ratio is maximum with the channel width of 3 nm for a gate length of 10 nm, but there is no significant effect of source and drain length on the current on-off ratio. The transconductance value plays a pivotal role in various electronic applications and should be considered carefully. In this research, it is also concluded that the transconductance value of 340 S/m is achieved with the fin width of 3 nm at a gate length of 10 nm and 2380 S/m for the source and drain extension length of 5 nm, respectively.

Keywords: current on-off ratio, FinFET, short-channel effects, transconductance

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10 Nutritional Status of Children in a Rural Food Environment, Haryana: A Paradox for the Policy Action

Authors: Neha Gupta, Sonika Verma, Seema Puri, Nikhil Tandon, Narendra K. Arora

Abstract:

The concurrent increasing prevalence of underweight and overweight/obesity among children with changing lifestyle and the rapid transitioning society has necessitated the need for a unifying/multi-level approach to understand the determinants of the problem. The present community-based cross-sectional research study was conducted to assess the associations between lifestyle behavior and food environment of the child at household, neighborhood, and school with the BMI of children (6-12 year old) (n=612) residing in three rural clusters of Palwal district, Haryana. The study used innovative and robust methods for assessing the lifestyle and various components of food environment in the study. The three rural clusters selected for the study were located at three different locations according to their access to highways in the SOMAARTH surveillance site. These clusters were significantly different from each other in terms of their socio-demographic and socio-economic profile, living conditions, environmental hygiene, health seeking behavior and retail density. Despite of being different, the quality of living conditions and environmental hygiene was poor across three clusters. The children had higher intakes of dietary energy and sugars; one-fifth share of the energy being derived from unhealthy foods, engagement in high levels of physical activity and significantly different food environment at home, neighborhood and school level. However, despite having a high energy intake, 22.5% of the recruited children were thin/severe thin, and 3% were overweight/obese as per their BMI-for-age categories. The analysis was done using multi-variate logistic regression at three-tier hierarchy including individual, household and community level. The factors significantly explained the variability in governing the risk of getting thin/severe thin among children in rural area (p-value: 0.0001; Adjusted R2: 0.156) included age (>10years) (OR: 2.1; 95% CI: 1.0-4.4), the interaction between minority category and poor SES of the household (OR: 4.4; 95% CI: 1.6-12.1), availability of sweets (OR: 0.9; 95% CI: 0.8-0.99) and cereals (OR: 0.9; 95% CI: 0.8-1.0) in the household and poor street condition (proxy indicator of the hygiene and cleanliness in the neighborhood) (OR: 0.3; 95% CI: 0.1-1.1). The homogeneity of other factors at neighborhood and school level food environment diluted the heterogeneity in the lifestyles and home environment of the recruited children and their households. However, it is evident that when various individual factors interplay at multiple levels amplifies the risk of undernutrition in a rural community. Conclusion: These rural areas in Haryana are undergoing developmental, economic and societal transition. In correspondence, no improvements in the nutritional status of children have happened. Easy access to the unhealthy foods has become a paradox.

Keywords: transition, food environment, lifestyle, undernutrition, overnutrition

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9 Optimal Uses of Rainwater to Maintain Water Level in Gomti Nagar, Uttar Pradesh, India

Authors: Alok Saini, Rajkumar Ghosh

Abstract:

Water is nature's important resource for survival of all living things, but freshwater scarcity exists in some parts of world. This study has predicted that Gomti Nagar area (49.2 sq. km.) will harvest about 91110 ML of rainwater till 2051 (assuming constant and present annual rainfall). But 17.71 ML of rainwater was harvested from only 53 buildings in Gomti Nagar area in the year 2021. Water level will be increased (rise) by 13 cm in Gomti Nagar from such groundwater recharge. The total annual groundwater abstraction from Gomti Nagar area was 35332 ML (in 2021). Due to hydrogeological constraints and lower annual rainfall, groundwater recharge is less than groundwater abstraction. The recent scenario is only 0.07% of rainwater recharges by RTRWHs in Gomti Nagar. But if RTRWHs would be installed in all buildings then 12.39% of rainwater could recharge groundwater table in Gomti Nagar area. But if RTRWHs would be installed in all buildings then 12.39% of rainwater could recharge groundwater table in Gomti Nagar area. Gomti Nagar is situated in 'Zone–A' (water distribution area) and groundwater is the primary source of freshwater supply. Current scenario indicates only 0.07% of rainwater recharges by RTRWHs in Gomti Nagar. In Gomti Nagar, the difference between groundwater abstraction and recharge will be 735570 ML in 30 yrs. Statistically, all buildings at Gomti Nagar (new and renovated) could harvest 3037 ML of rainwater through RTRWHs annually. The most recent monsoonal recharge in Gomti Nagar was 10813 ML/yr. Harvested rainwater collected from RTRWHs can be used for rooftop irrigation, and residential kitchen and gardens (home grown fruit and vegetables). According to bylaws, RTRWH installations are required in both newly constructed and existing buildings plot areas of 300 sq. m or above. Harvested rainwater is of higher quality than contaminated groundwater. Harvested rainwater from RTRWHs can be considered water self-sufficient. Rooftop Rainwater Harvesting Systems (RTRWHs) are least expensive, eco-friendly, most sustainable, and alternative water resource for artificial recharge. This study also predicts about 3.9 m of water level rise in Gomti Nagar area till 2051, only when all buildings will install RTRWHs and harvest for groundwater recharging. As a result, this current study responds to an impact assessment study of RTRWHs implementation for the water scarcity problem in the Gomti Nagar area (1.36 sq.km.). This study suggests that common storage tanks (recharge wells) should be built for a group of at least ten (10) households and optimal amount of harvested rainwater will be stored annually. Artificial recharge from alternative water sources will be required to improve the declining water level trend and balance the groundwater table in this area. This over-exploitation of groundwater may lead to land subsidence, and development of vertical cracks.

Keywords: aquifer, aquitard, artificial recharge, bylaws, groundwater, monsoon, rainfall, rooftop rainwater harvesting system, RTRWHs water table, water level

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8 Analysis of Non-Conventional Roundabout Performance in Mixed Traffic Conditions

Authors: Guneet Saini, Shahrukh, Sunil Sharma

Abstract:

Traffic congestion is the most critical issue faced by those in the transportation profession today. Over the past few years, roundabouts have been recognized as a measure to promote efficiency at intersections globally. In developing countries like India, this type of intersection still faces a lot of issues, such as bottleneck situations, long queues and increased waiting times, due to increasing traffic which in turn affect the performance of the entire urban network. This research is a case study of a non-conventional roundabout, in terms of geometric design, in a small town in India. These types of roundabouts should be analyzed for their functionality in mixed traffic conditions, prevalent in many developing countries. Microscopic traffic simulation is an effective tool to analyze traffic conditions and estimate various measures of operational performance of intersections such as capacity, vehicle delay, queue length and Level of Service (LOS) of urban roadway network. This study involves analyzation of an unsymmetrical non-circular 6-legged roundabout known as “Kala Aam Chauraha” in a small town Bulandshahr in Uttar Pradesh, India using VISSIM simulation package which is the most widely used software for microscopic traffic simulation. For coding in VISSIM, data are collected from the site during morning and evening peak hours of a weekday and then analyzed for base model building. The model is calibrated on driving behavior and vehicle parameters and an optimal set of calibrated parameters is obtained followed by validation of the model to obtain the base model which can replicate the real field conditions. This calibrated and validated model is then used to analyze the prevailing operational traffic performance of the roundabout which is then compared with a proposed alternative to improve efficiency of roundabout network and to accommodate pedestrians in the geometry. The study results show that the alternative proposed is an advantage over the present roundabout as it considerably reduces congestion, vehicle delay and queue length and hence, successfully improves roundabout performance without compromising on pedestrian safety. The study proposes similar designs for modification of existing non-conventional roundabouts experiencing excessive delays and queues in order to improve their efficiency especially in the case of developing countries. From this study, it can be concluded that there is a need to improve the current geometry of such roundabouts to ensure better traffic performance and safety of drivers and pedestrians negotiating the intersection and hence this proposal may be considered as a best fit.

Keywords: operational performance, roundabout, simulation, VISSIM

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7 Traumatic Brain Injury Induced Lipid Profiling of Lipids in Mice Serum Using UHPLC-Q-TOF-MS

Authors: Seema Dhariwal, Kiran Maan, Ruchi Baghel, Apoorva Sharma, Poonam Rana

Abstract:

Introduction: Traumatic brain injury (TBI) is defined as the temporary or permanent alteration in brain function and pathology caused by an external mechanical force. It represents the leading cause of mortality and morbidity among children and youth individuals. Various models of TBI in rodents have been developed in the laboratory to mimic the scenario of injury. Blast overpressure injury is common among civilians and military personnel, followed by accidents or explosive devices. In addition to this, the lateral Controlled cortical impact (CCI) model mimics the blunt, penetrating injury. Method: In the present study, we have developed two different mild TBI models using blast and CCI injury. In the blast model, helium gas was used to create an overpressure of 130 kPa (±5) via a shock tube, and CCI injury was induced with an impact depth of 1.5mm to create diffusive and focal injury, respectively. C57BL/6J male mice (10-12 weeks) were divided into three groups: (1) control, (2) Blast treated, (3) CCI treated, and were exposed to different injury models. Serum was collected on Day1 and day7, followed by biphasic extraction using MTBE/Methanol/Water. Prepared samples were separated on Charged Surface Hybrid (CSH) C18 column and acquired on UHPLC-Q-TOF-MS using ESI probe with inhouse optimized parameters and method. MS peak list was generated using Markerview TM. Data were normalized, Pareto-scaled, and log-transformed, followed by multivariate and univariate analysis in metaboanalyst. Result and discussion: Untargeted profiling of lipids generated extensive data features, which were annotated through LIPID MAPS® based on their m/z and were further confirmed based on their fragment pattern by LipidBlast. There is the final annotation of 269 features in the positive and 182 features in the negative mode of ionization. PCA and PLS-DA score plots showed clear segregation of injury groups to controls. Among various lipids in mild blast and CCI, five lipids (Glycerophospholipids {PC 30:2, PE O-33:3, PG 28:3;O3 and PS 36:1 } and fatty acyl { FA 21:3;O2}) were significantly altered in both injury groups at Day 1 and Day 7, and also had VIP score >1. Pathway analysis by Biopan has also shown hampered synthesis of Glycerolipids and Glycerophospholipiods, which coincides with earlier reports. It could be a direct result of alteration in the Acetylcholine signaling pathway in response to TBI. Understanding the role of a specific class of lipid metabolism, regulation and transport could be beneficial to TBI research since it could provide new targets and determine the best therapeutic intervention. This study demonstrates the potential lipid biomarkers which can be used for injury severity diagnosis and identification irrespective of injury type (diffusive or focal).

Keywords: LipidBlast, lipidomic biomarker, LIPID MAPS®, TBI

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6 Endometrial Biopsy Curettage vs Endometrial Aspiration: Better Modality in Female Genital Tuberculosis

Authors: Rupali Bhatia, Deepthi Nair, Geetika Khanna, Seema Singhal

Abstract:

Introduction: Genital tract tuberculosis is a chronic disease (caused by reactivation of organisms from systemic distribution of Mycobacterium tuberculosis) that often presents with low grade symptoms and non-specific complaints. Patients with genital tuberculosis are usually young women seeking workup and treatment for infertility. Infertility is the commonest presentation due to involvement of the fallopian tubes, endometrium and ovarian damage with poor ovarian volume and reserve. The diagnosis of genital tuberculosis is difficult because of the fact that it is a silent invader of genital tract. Since tissue cannot be obtained from fallopian tubes, the diagnosis is made by isolation of bacilli from endometrial tissue obtained by endometrial biopsy curettage and/or aspiration. Problems are associated with sampling technique as well as diagnostic modality due to lack of adequate sample volumes and the segregation of the sample for various diagnostic tests resulting in non-uniform distribution of microorganisms. Moreover, lack of an efficient sampling technique universally applicable for all specific diagnostic tests contributes to the diagnostic challenges. Endometrial sampling plays a key role in accurate diagnosis of female genital tuberculosis. It may be done by 2 methods viz. endometrial curettage and endometrial aspiration. Both endometrial curettage and aspirate have their own limitations as curettage picks up strip of the endometrium from one of the walls of the uterine cavity including tubal osteal areas whereas aspirate obtains total tissue with exfoliated cells present in the secretory fluid of the endometrial cavity. Further, sparse and uneven distribution of the bacilli remains a major factor contributing to the limitations of the techniques. The sample that is obtained by either technique is subjected to histopathological examination, AFB staining, culture and PCR. Aim: Comparison of the sampling techniques viz. endometrial biopsy curettage and endometrial aspiration using different laboratory methods of histopathology, cytology, microbiology and molecular biology. Method: In a hospital based observational study, 75 Indian females suspected of genital tuberculosis were selected on the basis of inclusion criteria. The women underwent endometrial tissue sampling using Novaks biopsy curette and Karmans cannula. One part of the specimen obtained was sent in formalin solution for histopathological testing and another part was sent in normal saline for acid fast bacilli smear, culture and polymerase chain reaction. The results so obtained were correlated using coefficient of correlation and chi square test. Result: Concordance of results showed moderate agreement between both the sampling techniques. Among HPE, AFB and PCR, maximum sensitivity was observed for PCR, though the specificity was not as high as other techniques. Conclusion: Statistically no significant difference was observed between the results obtained by the two sampling techniques. Therefore, one may use either EA or EB to obtain endometrial samples and avoid multiple sampling as both the techniques are equally efficient in diagnosing genital tuberculosis by HPE, AFB, culture or PCR.

Keywords: acid fast bacilli (AFB), histopatholgy examination (HPE), polymerase chain reaction (PCR), endometrial biopsy curettage

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5 Weaving Social Development: An Exploratory Study of Adapting Traditional Textiles Using Indigenous Organic Wool for the Modern Interior Textiles Market

Authors: Seema Singh, Puja Anand, Alok Bhasin

Abstract:

The interior design profession aims to create aesthetically pleasing design solutions for human habitats but of late, growing awareness about depleting environmental resources, both tangible and intangible, and damages to the eco-system led to the quest for creating healthy and sustainable interior environments. The paper proposes adapting traditionally produced organic wool textiles for the mainstream interior design industry. This can create sustainable livelihoods whereby eco-friendly bridges can be built between Interior designers and consumers and pastoral communities. This study focuses on traditional textiles produced by two pastoral communities from India that use organic wool from indigenous sheep varieties. The Gaddi communities of Himachal Pradesh use wool from the Gaddi sheep breed to create Pattu (a multi-purpose textile). The Kurumas of Telangana weave a blanket called the Gongadi, using wool from the Black Deccani variety of sheep. These communities have traditionally reared indigenous sheep breeds for their wool and produce hand-spun and hand-woven textiles for their own consumption, using traditional processes that are chemical free. Based on data collected personally from field visits and documentation of traditional crafts of these pastoral communities, and using traditionally produced indigenous organic wool, the authors have developed innovative textile samples by including design interventions and exploring dyeing and weaving techniques. As part of the secondary research, the role of pastoralism in sustaining the eco-systems of Himachal Pradesh and Telangana was studied, and also the role of organic wool in creating healthy interior environments. The authors found that natural wool from indigenous sheep breeds can be used to create interior textiles that have the potential to be marketed to an urban audience, and this will help create earnings for pastoral communities. Literature studies have shown that organic & sustainable wool can reduce indoor pollution & toxicity levels in interiors and further help in creating healthier interior environments. Revival of indigenous breeds of sheep can further help in rejuvenating dying crafts, and promotion of these indigenous textiles can help in sustaining traditional eco-systems and the pastoral communities whose way of life is endangered today. Based on research and findings, the authors propose that adapting traditional textiles can have potential for application in Interiors, creating eco-friendly spaces. Interior textiles produced through such sustainable processes can help reduce indoor pollution, give livelihood opportunities to traditional economies, and leave almost zero carbon foot-print while being in sync with available natural resources, hence ultimately benefiting the society. The win-win situation for all the stakeholders in this eco-friendly model makes it pertinent to re-think how we design lifestyle textiles for interiors. This study illustrates a specific example from the two pastoral communities and can be used as a model that can work equally well in any community, regardless of geography.

Keywords: design intervention, eco- friendly, healthy interiors, indigenous, organic wool, pastoralism, sustainability

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4 Testicular Differential MicroRNA Expression Derived Occupational Risk Factor Assessment in Idiopathic Non-obstructive Azoospermia Cases

Authors: Nisha Sharma, Mili Kaur, Ashutosh Halder, Seema Kaushal, Manoj Kumar, Manish Jain

Abstract:

Purpose: To investigate microRNAs (miRNA) as an epigenomic etiological factor in idiopathic non-obstructive azoospermia (NOA). In order to achieve the same, an association was seen between occupational exposure to radiation, thermal, and chemical factors and idiopathic cases of non-obstructive azoospermia, and later, testicular differential miRNA expression profiling was done in exposure group NOA cases. Method: It is a prospective study in which 200 apparent idiopathic male factor infertility cases, who have been advised to undergo testicular fine needle aspiration (FNA) evaluation, are recruited. A detailed occupational history was taken to understand the possible type of exposure due to the nature and duration of work. A total of 26 patients were excluded upon XY-FISH and Yq microdeletion tests due to the presence of genetic causes of infertility, 6 hypospermatogeneis (HS), six Sertoli cell-only syndrome (SCOS), and six normospermatogeneis patients testicular FNA samples were used for RNA isolation followed by small RNA sequencing and nCounter miRNA expression analysis. Differential miRNA expression profile of HS and SCOS patients was done. A web-based tool, miRNet, was used to predict the interacting compounds or chemicals using the shortlisted miRNAs with high fold change. The major limitation encountered in this study was the insufficient quantity of testicular FNA sample used for total RNA isolation, which resulted in a low yield and RNA integrity number (RIN) value. Therefore, the number of RNA samples admissible for differential miRNA expression analysis was very small in comparison to the total number of patients recruited. Results: Differential expression analysis revealed 69 down-regulated and 40 up-regulated miRNAs in HS and 66 down-regulated and 33 up-regulated miRNAs in SCOS in comparison to normospermatogenesis controls. The miRNA interaction analysis using the miRNet tool showed that the differential expression profiles of HS and SCOS patients were associated with arsenic trioxide, bisphenol-A, calcium sulphate, lithium, and cadmium. These compounds are reproductive toxins and might be responsible for miRNA-mediated epigenetic deregulation leading to NOA. The association between occupational risk factor exposure and the non-exposure group of NOA patients was not statistically significant, with ꭓ2 (3, N= 178) = 6.70, p= 0.082. The association between individual exposure groups (radiation, thermal, and chemical) and various sub-types of NOA is also not significant, with ꭓ2 (9, N= 178) = 15.06, p= 0.089. Functional analysis of HS and SCOS patients' miRNA profiles revealed some important miR-family members in terms of male fertility. The miR-181 family plays a role in the differentiation of spermatogonia and spermatocytes, as well as the transcriptional regulation of haploid germ cells. The miR-34 family is expressed in spermatocytes and round spermatids and is involved in the regulation of SSCs differentiation. Conclusion: The reproductive toxins might adopt the miRNA-mediated mechanism of disease development in idiopathic cases of NOA. Chemical compound induced; miRNA-mediated epigenetic deregulation can give a future perspective on the etiopathogenesis of the disease.

Keywords: microRNA, non-obstructive azoospermia (NOA), occupational exposure, hypospermatogenesis (HS), Sertoli cell only syndrome (SCOS)

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3 Development and Evaluation of Economical Self-cleaning Cement

Authors: Anil Saini, Jatinder Kumar Ratan

Abstract:

Now a day, the key issue for the scientific community is to devise the innovative technologies for sustainable control of urban pollution. In urban cities, a large surface area of the masonry structures, buildings, and pavements is exposed to the open environment, which may be utilized for the control of air pollution, if it is built from the photocatalytically active cement-based constructional materials such as concrete, mortars, paints, and blocks, etc. The photocatalytically active cement is formulated by incorporating a photocatalyst in the cement matrix, and such cement is generally known as self-cleaning cement In the literature, self-cleaning cement has been synthesized by incorporating nanosized-TiO₂ (n-TiO₂) as a photocatalyst in the formulation of the cement. However, the utilization of n-TiO₂ for the formulation of self-cleaning cement has the drawbacks of nano-toxicity, higher cost, and agglomeration as far as the commercial production and applications are concerned. The use of microsized-TiO₂ (m-TiO₂) in place of n-TiO₂ for the commercial manufacture of self-cleaning cement could avoid the above-mentioned problems. However, m-TiO₂ is less photocatalytically active as compared to n- TiO₂ due to smaller surface area, higher band gap, and increased recombination rate. As such, the use of m-TiO₂ in the formulation of self-cleaning cement may lead to a reduction in photocatalytic activity, thus, reducing the self-cleaning, depolluting, and antimicrobial abilities of the resultant cement material. So improvement in the photoactivity of m-TiO₂ based self-cleaning cement is the key issue for its practical applications in the present scenario. The current work proposes the use of surface-fluorinated m-TiO₂ for the formulation of self-cleaning cement to enhance its photocatalytic activity. The calcined dolomite, a constructional material, has also been utilized as co-adsorbent along with the surface-fluorinated m-TiO₂ in the formulation of self-cleaning cement to enhance the photocatalytic performance. The surface-fluorinated m-TiO₂, calcined dolomite, and the formulated self-cleaning cement were characterized using diffuse reflectance spectroscopy (DRS), X-ray diffraction analysis (XRD), field emission-scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), BET (Brunauer–Emmett–Teller) surface area, and energy dispersive X-ray fluorescence spectrometry (EDXRF). The self-cleaning property of the as-prepared self-cleaning cement was evaluated using the methylene blue (MB) test. The depolluting ability of the formulated self-cleaning cement was assessed through a continuous NOX removal test. The antimicrobial activity of the self-cleaning cement was appraised using the method of the zone of inhibition. The as-prepared self-cleaning cement obtained by uniform mixing of 87% clinker, 10% calcined dolomite, and 3% surface-fluorinated m-TiO₂ showed a remarkable self-cleaning property by providing 53.9% degradation of the coated MB dye. The self-cleaning cement also depicted a noteworthy depolluting ability by removing 5.5% of NOx from the air. The inactivation of B. subtiltis bacteria in the presence of light confirmed the significant antimicrobial property of the formulated self-cleaning cement. The self-cleaning, depolluting, and antimicrobial results are attributed to the synergetic effect of surface-fluorinated m-TiO₂ and calcined dolomite in the cement matrix. The present study opens an idea and route for further research for acile and economical formulation of self-cleaning cement.

Keywords: microsized-titanium dioxide (m-TiO₂), self-cleaning cement, photocatalysis, surface-fluorination

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2 Correlation Analysis of Reactivity in the Oxidation of Para and Meta-Substituted Benzyl Alcohols by Benzimidazolium Dichromate in Non-Aqueous Media: A Kinetic and Mechanistic Aspects

Authors: Seema Kothari, Dinesh Panday

Abstract:

An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

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1 Relationship between Illegal Wildlife Trade and Community Conservation: A Case Study of the Chepang Community in Nepal

Authors: Vasundhara H. Krishnani, Ajay Saini, Dibesh Karmacharya, Salit Kark

Abstract:

Illegal Wildlife Trade is one of the most pressing global conservation challenges. Unregulated wildlife trade can threaten biodiversity, contribute to habitat loss, limit sustainable development efforts, and expedite species declines and extinctions. In low-income and middle-income countries, such as Nepal and other countries in Asia and Africa, many of the people engaged in the early stages of illegal wildlife trade, which includes the hunting and transportation of wildlife, belong to Indigenous tribes and local communities.These countries primarily rely on punitive measures to prevent and suppress Illegal Wildlife Trade. For example, in Nepal, people involved in wildlife crimes can often be sentenced to incarceration and a hefty fine and serve up to 15 years in prison. Despite these harsh punitive measures, illegal wildlife trade remains a significant conservation challenge in many countries. The aim of this study was to examine factors affecting the participation of Indigenous communities in Illegal Wildlife Trade while recording the experiences of members of the Indigenous Chepang community, some of whom were imprisoned for their alleged involvement in rhino poaching. Chepangs, belonging to traditionally a hunter-gatherer community, are often considered an isolated and marginalized Indigenous community, some of whom live around the Chitwan National Park in Nepal. Established in 1973, Chitwan National Park is situated in the Chitwan Valley of Nepal and was one of the first regions that was declared as a protected area in Nepal, aiming to protect the one-horned rhinoceros as a flagship species. Conducted over a period of three years, this study used semi-structured interviews and focus group discussions to collect data from Illegal Wildlife Trade offenders, family members of offenders, community Elders, NGO personnel, community forest representatives, Chepang community representatives, and Government school teachers from the region surrounding Chitwan National Park. The study also examined the social, cultural, health, and financial impacts that the imprisonment of offenders had on the families of the community members, especially women and children. The results suggest that involvement of the members of the Chepang community living around Chitwan National Park in the poaching of the one-horned rhinoceros (Rhinoceros unicornis) can be attributed to a range of factors, some of which include: lack of livelihood opportunities, lack of awareness regarding wildlife rules and regulations and poverty.This work emphasises the need for raising awareness and building programs to enhance alternative livelihood training and empower indigenous and marginalised communities that provide sustainable alternatives. Furthermore, the issue needs to be addressed as a community solution which includes all community members. We suggest this multi-pronged approach can benefit wildlife conservation by reducing illegal poaching and wildlife trade, as well as community conservation in regions with similar challenges. By actively involving and empowering local communities, the communities become key stakeholders in the conservation process. This involvement contributes to protecting wildlife and natural ecosystems while simultaneously providing sustainable livelihood options for local communities.

Keywords: alternative livelihoods, chepang community, illegal wildlife trade, low-and middle-income countries, nepal, one-horned rhinoceros

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