Design, Synthesis of 3-(Aryl)-1-(2-p-tolylthiazol-4-yl)prop-2-en-1-ones as Alpha(α)-Amylase Inhibitors.

α-Amylase inhibition is vital in controlling diabetic complications. Herein, we have synthesized a hybrid scaffold based on thiazole-chalcone to access α-amylase inhbition. The proposed structures were verified with spectroscopic techniques (UV-vis, FT-IR, 1H-, 13C-NMR, and elemental analysis). The synthesized compounds were evaluated for their α-amylase and antioxidant potential. In vitro hemolytic assay was performed to test biocompatibility of all compounds. Among tested compounds, 4c (IC50= 3.8 µM), 4g (IC50= 14.5 µM), and 4f (IC50= 17.1 µM) were found excellent α-amylase inhibitors. However, none of the tested compounds exhibited significant antioxidant activity. All compounds showed less lysis than Triton X-100, but compounds 4f and 4h had the least lysis at all tested concentrations and were found to be safe for human erythrocytes. Molecular docking study was performed to evaluate the binding interactions of ligands with human pancreatic α-amylase (HPA). The binding score -8.09 to -8.507 kcal/mol revealed strong binding interactions in the ligand-protein complex. The docking results supplemented the observed α-amylase inhibition and hence augment the scaffold to serve as leads for the antidiabetic drug development.

Long-term proton pump inhibitors therapy and prevalence of hyperprolactinaemia: A cross-sectional study in outpatient gastroenterology clinics.

Objectives: To evaluate serum prolactin and macroprolactin levels in patients on long-term proton pump inhibitors therapy. METHODS: The cross-sectional study was conducted from January 2018 to November 2019 after approval from the ethics review committee of the Commission on Science and Technology for Sustainable Development in the South University, Abbottabad, Pakistan. The study included patients from two gastroenterology outpatient clinics in the Khyber Pakhtunkhwa province using proton pump inhibitors for ≥3 months either alone or in combination with either histamine receptor antagonists or prokinetics. Blood samples were collected from each patient for hormonal screening. Data was analysed using SPSS 25. RESULTS: Of the 166 patients, 101(60.8%) were females and 65(39.2%) were males. The overall mean age was 42.5±14.2 years, and the median serum prolactin level was 23.2ng/ml (interquartile range: 14.0-38.0ng/ml). There were 96(58%) patients with normoprolactinaemia and 70(42%) with hypreprolactinaemia. There were 19(11.4%) patients using combination therapy, while the rest were on proton pump inhibitors monotherapy. There was a significant increase in serum prolactin level with combination therapy compared to monotherapy (p=0.001). Patients having treatment duration 11-20 months (p=0.006) and >40 months (p=0.001) were at high risk of developing hyperprolactinaemia. CONCLUSIONS: Long-term use of proton pump inhibitors could increase serum prolactin levels, and appropriate evaluation is essential for clinical management.

Assessing rural land use in contemporary China: Data compilation and methodology.

In rural areas, land use decisions are not only shaped by economic considerations but also deeply influenced by cultural and social factors. The objective of this research is to examine the complex and diverse aspects of making decisions about how land is used in rural communities, specifically by investigating the influence of cultural and social elements. Using empirical data and rigorous analysis, this research examine how traditional practices, social norms, and community dynamics influence land use patterns. The research topic focuses on the need to have a thorough understanding of the fundamental elements that affect land use choices in rural regions, going beyond only economic incentives. This research objective is to address a significant vacuum in the current literature by examining the cultural and social aspects of land usage. This research provides vital insights for policymakers and stakeholders engaged in land management and rural development projects. This research utilizes a mixed-methods approach, using qualitative interviews, participatory observations, and quantitative surveys to collect comprehensive data on the cultural and socioeconomic elements that impact land use choices. The research sample includes a wide range of rural areas, guaranteeing a thorough representation of various cultural settings and socioeconomic backgrounds. Our study reveals that cultural traditions, social networks, and power structures have a substantial impact on land use practices in rural regions. Traditional land tenure systems, community ownership arrangements, and customary land-use practices play a vital role in influencing land-use choices and resource distribution within communities. The significance of these results is substantial for policymakers, land managers, and rural development practitioners. Policymakers may create land use policies and actions that are more appropriate to the specific cultural and socioeconomic environment by understanding the complex relationship between these aspects. Furthermore, promoting community involvement and allowing local actors to participate in decision-making may result in land management results that are both more sustainable and fair.

Synthesis, anti-diabetic profiling and molecular docking studies of 2-(2-arylidenehydrazinyl)thiazol-4(5H)-ones.

Aim: To synthesize novel more potent anti-diabetic agents. Methodology: A simple cost effective Hantzsch's synthetic strategy was used to synthesize 2-(2-arylidenehydrazinyl)thiazol-4(5H)-ones. Results: Fifteen new 2-(2-arylidenehydrazinyl)thiazol-4(5H)-ones were established to check their anti-diabetic potential. From alpha(α)-amylase inhibition, anti-glycation and anti-oxidant activities it is revealed that most of the compounds possess good anti-diabetic potential. All tested compounds were found to be more potent anti-diabetic agents via anti-glycation mode. The results of α-amylase and anti-oxidant inhibition revealed that compounds are less active against α-amylase and anti-oxidant assays. Conclusion: This study concludes that introduction of various electron withdrawing groups at the aryl ring and substitution of different functionalities around thiazolone nucleus could help to find out better anti-diabetic drug.

Diabetes is a most spreading chronicle disease effecting millions of peoples across the globe every year and this number increases day by day. To cure the human population from this dilemma, we had synthesized, characterized and evaluated the anti-diabetic behavior of our synthesized compounds. α-Amylase, in vitro anti-glycation and anti-oxidant assays were performed to find out good lead for Diabetes Mellitus. All tested compounds were found to be excellent anti-glycating agents with IC₅₀ values far better than standard amino-guanidine (IC₅₀ = 3.582 ± 0.002 µM). Compound 4m was most efficient glycation inhibitor (IC₅₀ = 1.095 ± 0.002 µM). Cytotoxicity of all compounds was determined with in vitro hemolytic assay and found all compounds safe and bio-compatible to humans at all tested concentrations. The inhibition potential was also examined with theoretical docking studies to support our experimental results against human pancreatic alpha-amylase (HPA) and human serum albumin (HSA) proteins. All compounds showed excellent binding affinity with HSA active pockets however, only compound 4h and 4k binding affinity was good with HPA.

Consumption of proton pump inhibitors in outpatients of Gastroenterology Clinics in Khyber Pakhtunkhwa: evidence of inexpedient use.

Introduction: Proton pump inhibitors (PPIs) are effective drugs used for multiple gastrointestinal complications. They are commonly used in both hospitalised and outpatients. However, little is known about its utilisation pattern in ambulatory patients. Aim: To evaluate the inexpedient continuous use of PPIs in patients with respect to treatment duration. Material and methods: A cross-sectional observational study was conducted from January 2018 to November 2019 in Khyber Pakhtunkhwa, Pakistan. Regular proton pump inhibitor users were identified through patient histories. Results: During the study period, 171 patients were included using a non-probability consecutive sampling technique, who were using regular proton pump inhibitors for a longer duration, i.e. from 3 months to 15 years. The highest proportion (42.8%) were using PPI regularly from 3 months to 1 year followed by 22.9% for 1-2 years, 12.0% for 2-3 years, 7.8% for 3-4 years, 4.2% for 4-5 years, and 10.24% for > 5 years. Omeprazole and esomeprazole were the most commonly used drugs, with 71.1% and 23.5% prevalence, respectively. A total of 33.73% of patients had continued PPI use on their own after initially being prescribed by the physician. Conclusions: It can be deduced that PPIs are used in outpatients beyond standard treatment guidelines. The inexpedient continuous use of proton pump inhibitors is of concern due to the risk of developing adverse effects. Therefore, patient counselling and periodic monitoring must be carried out to prevent the irrational use of PPIs.

A first principles based prediction of electronic and nonlinear optical properties towards cyclopenta thiophene chromophores with benzothiophene acceptor moieties.

In the current work, organic cyclopenta-thiophene (CPT) based derivatives (FICR and FICD1-FICD5) were designed by the modulation of end-capped acceptor group of the reference molecule i.e., FICR, to explore their nonlinear optical (NLO) response. The effect of terminal acceptor and donor groups in the tailored compounds was explored by using DFT based quantum calculations. The UV-Vis analysis, frontier molecular orbitals (FMOs), transition density matrix (TDM), natural bond orbitals (NBOs), density of states (DOS), nonlinear optical (NLO) analyses were performed at M06/6-311G(d,p) functional. The LUMO-HOMO band gaps of FICD1-FICD5 were found to be smaller (1.75-1.92 eV) comparative to FICR (1.98 eV). Moreover, the global reactivity parameters (GRPs) were correlated with the results of other analyses. FICD2 and FICD5 with lowest band gap 1.73 and 1.75 eV showed less hardness (0.86 and 0.87 eV, respectively), high softness (0.58 and 0.57 eV-1), and larger absorption spectrum (815 and 813 nm) in gaseous phase and (889 and 880 nm) in solvent phase among all entitled compounds. All the designed chromophores (FICD1-FICD5) demonstrated a significant NLO response as compared to FICR. Particularly, FICD2 and FICD5 exhibited the highest average linear polarizability (<α>) [2.86 × 10-22 and 2.88 × 10-22 esu], first hyperpolarizability (ßtot) (8.43 × 10-27 and 8.35 × 10-27 esu) and second hyperpolarizability (γtot) (13.20 × 10-32 and 13.0 × 10-32 esu) values as compared to the other derivatives. In nutshell, structural modeling of CPT based chromophores with extended acceptors, can be significantly utilized to achieve potential NLO materials.

Evidence from China's shipping sector on the impact of fiscal measures in enabling a low-carbon economic transition.

The Green Economy Initiative aims to achieve economic development while minimizing carbon emissions by implementing a low-carbon economy across all sectors. It is noteworthy that ships play a significant role in global commodity transportation, accounting for approximately 80-90 percent. However, this also leads to a surge in fossil fuel consumption and alarming pollution levels. The data utilized in this article spans from 2010 to 2022 and specifically focuses on the shipping industry, drawing from information collected in 20 different provinces of China. Multiple panel regression models were constructed to analyze the influence of fiscal policies on facilitating the transition toward a low-carbon economy. In addition, a vector autoregression model was employed to examine the interconnected dynamics between low-carbon transition and budgetary guidelines. The findings indicate that tax-based policies demonstrate an inverted U-shaped relationship with low-carbon transition, whereas transfer payment policies exhibit an N-shaped pattern. The shipping sector is actively embracing low-carbon practices, largely due to incorporating digital technologies that mitigate the adverse impacts of fiscal regulations.

How causality impacts the renewable energy, carbon emissions, and economic growth nexus in the South Caucasus Countries?

Renewable energy is essential for boosting economic expansion and lowering carbon dioxide emission (CO2) to achieve carbon neutrality. This study's objective is to investigate the relationship between the use of renewable energy, economic growth, and CO2 for South Caucasus Countries. For analysis purposes, time series methods were applied on the panel data. Second-generation unit root and cointegration tests were used to test the cross-sectional dependence. Afterward, panel causality and panel VAR techniques were performed to examine the relationship between the variables. Based on feedback hypothesis, results of our causality analysis revealed a bidirectional causality relationship between growth and renewable energy consumption. Moreover, we revealed unidirectional causality from CO2 to renewable energy and from growth to CO2 emission. We also found that the effect of a shock in renewable energy on growth is increasing, and on CO2, it is decreasing implying that renewable energy consumption will trigger growth and have a reducing effect on CO2 emissions. We portrayed significant workable implications for policymakers, regulation bodies, companies, stakeholders, and managers. Results from this study should be extrapolated with caution since their applicability is limited to the South Caucasus Countries. In addition, the research heavily depends on summaries, which may obscure regional differences. In the future, researchers may want to dig deeper into the data and examine the subtle effect of renewable energy policy nationally. Moreover, including socio-economic aspects and technical improvements in the research might give a more thorough picture of the dynamics at play.

Performance of angle shear connectors for U-shaped steel concrete infilled composite beams.

The current design codes i.e. AISC 360-16, CSA-S16-19, EC-04 etc. provide empirical relationships to estimate the capacity of shear connectors which were developed based on pushout tests of headed studs and channels connectors in exposed type sections. Therefore, these equations may result inaccurate predictions for strength of connectors in infilled-type sections. This study presents a detailed experimental study investigating the performance of angle connectors in composite sections. The testing program consisted two series of pushout tests. A total of 36 specimens were tested, considering the influence of several important parameters i.e. the length (Lc), height (hc), and web-thickness (tw) of angle connector, length of the weld (w) and the direction of shear connector (forward/backward) etc. The tests results demonstrated that with increasing connector height hs, and thickness, the maximum load Pmax and slip δu were increased. The connector direction didn't change much the load-slip behavior. The prediction accuracy of the existing shear capacity models was evaluated by comparing the predictions with experimental results. The current equations were noticed to be highly inconsistent in predicting the shear capacity of angle connectors, especially in case of infilled type sections. When the entire length of connector was taken as the effective length, the models overestimated the shear capacity. While in case when the welding length was taken as effective length in calculations, the models underestimated the shear strength of angle connectors.

Synthesis of hydrazinyl-thiazole ester derivatives, in vitro trypanocidal and leishmanicidal activities.

Aim: To synthesize novel more potent trypanocidal and leishmanicidal agents. Methods: Hantzsch's synthetic strategy was used to synthesize 1,3-thiazole-4-carboxylates and their N-benzylated derivatives. Results: 28 new thiazole-carboxylates and their N-benzylated derivatives were established to test their trypanocidal and leishmanicidal activities. From both series, compounds 3b, 4f, 4g, 4j and 4n exhibited a better or comparable trypanocidal profile to benznidazole. Among all tested compounds, 4n was found to be the most potent and was better than benznidazole. Conclusion: Further variation of substituents around 1,3-thiazole-4-carboxylates and or hydrazinyl moiety may assist in establishing better and more potent trypanocidal and leishmanicidal agents.

Chagas disease and leishmaniasis are neglected tropical diseases. Herein, 28 1,3-thiazoles have been synthesized from thiosemicarbazones in a rapid, efficient and cost-effective manner. In vitro assays were performed against intracellular amastigotes of Trypanosoma cruzi (T. cruzi) and promastigotes and intracellular amastigote forms of Leishmania infantum (L. infantum) and Leishmania amazonensis (L. amazonensis). Some of the 1,3-thiazole-4-carboxylates inhibited the amastigote form of T. cruzi without affecting macrophage viability, compound 4n being the most potent and better than benznidazole. Our synthesized compounds exhibited promising activity against T. cruzi, thus broadening options for scaffold and lead compound optimization. Concerning the leishmanicidal activity, compound 4g was the best prototype in terms of potency and selectivity. Compounds 4g and 3m showed moderate selectivity and potency against intracellular amastigotes of L. amazonensis and L. infantum, respectively.

Effects of long-term proton pump inhibitor use on sexual hormones and sexual and reproductive health in female patients.

PURPOSE: Proton pump inhibitors (PPIs) are widely used to treat a range of gastrointestinal diseases around the world. Long-term use of PPIs has been associated to a variety of undesirable effects. Although short-term therapy has been shown to have little or no effect on endocrine hormone in women, however, its long-term safety has received little attention. We aimed at evaluating long-term use of PPIs and its effects on female reproductive hormones as well as related clinical consequences. METHODS: A cross-sectional study was conducted in two outpatient gastroenterology clinics in the province of Khyber Pakhtunkhwa. This study included female patients who had been using PPIs on a regular basis for 3 months or more. RESULTS: In total of 101 participants, patients with sexual complaints have significantly altered levels of prolactin (p = 0.05), estrogen (p < 0.001) and progesterone (p = 0.001) than patient without sexual complaints. The frequency of amenorrhea (p < 0.001), cyclic disturbances (p < 0.001), breast augmentation (p = 0.001) and painful breast (p = 0.004) were statistically significant in patients with raised serum prolactin values. Serum values of Sex hormone binding globulin SHBG (p < 0.001), estradiol (p = 0.002) and total testosterone (p < 0.001) were significantly altered between normal prolactin and hyperprolactinemic patients. CONCLUSION: These findings suggest that long-term PPI use may cause endocrine hormone disturbances leading to sexual difficulties in women.

Auditing YouTube's recommendation system for ideologically congenial, extreme, and problematic recommendations.

Algorithms of social media platforms are often criticized for recommending ideologically congenial and radical content to their users. Despite these concerns, evidence on such filter bubbles and rabbit holes of radicalization is inconclusive. We conduct an audit of the platform using 100,000 sock puppets that allow us to systematically and at scale isolate the influence of the algorithm in recommendations. We test 1) whether recommended videos are congenial with regard to users' ideology, especially deeper in the watch trail and whether 2) recommendations deeper in the trail become progressively more extreme and come from problematic channels. We find that YouTube's algorithm recommends congenial content to its partisan users, although some moderate and cross-cutting exposure is possible and that congenial recommendations increase deeper in the trail for right-leaning users. We do not find meaningful increases in ideological extremity of recommendations deeper in the trail, yet we show that a growing proportion of recommendations comes from channels categorized as problematic (e.g., "IDW," "Alt-right," "Conspiracy," and "QAnon"), with this increase being most pronounced among the very-right users. Although the proportion of these problematic recommendations is low (max of 2.5%), they are still encountered by over 36.1% of users and up to 40% in the case of very-right users.

The influence of environment and Earnings on Prolonged existence and human fertility: A Deeper Dive into Asia's environmentally vulnerable nations.

This study inspects the impact of environmental deterioration and income on longevity and fertility in Asian countries, specifically the nations that are highly vulnerable to extreme weather. The study examines the data, covering two decades from 2000 to 2019. The empirical conclusions of the panel ARDL-PMG and the CS-ARDL econometric models indicate that environmental degradation leads to a decline in birth rate and life expectancy, while a rising income has a significant influence over longevity. However, increasing per capita income alone cannot solve the problem of population crisis in climatically susceptible countries. Therefore, the sample countries must prioritize climate action and formulate climate-resilient policies to add more years to the lives of their citizens. Similarly, for increasing childbirth the sample nations need to make peace with nature. The outcomes of this study are strong enough, as both the models support each other's findings, producing similar significant outcomes.

Promising impact of push-pull configuration into designed octacyclic naphthalene-based organic scaffolds for nonlinear optical amplitudes: a quantum chemical approach.

In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1-D9) with D-π-A configuration from PCMR. DFT analysis at M06/6-311G (d,p) level was accomplished to explore the photonic behavior of PCMD1-D9 compounds. Various kind of analysis like; UV-Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1 with the least band gap of 2.048 eV in PCMD8 among all the compounds. The UV-Visible spectrum of the entitled chromophores manifested high values of λmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization (34.31 kcal/mol) for PCMD8 chromophore. The highest linear polarizability (<α>) and dipole moment (µtot) values were exhibited by PCMD5 at 2.712 × 10-22. and 1.995 × 10-17 esu, respectively. PCMD8 push-pull configured molecular entity exhibited highest first hyper-polarizability (ßtot) at 4.747 × 10-27 esu and second hyper-polarizability at 6.867 × 10-32 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.

Are the healthcare providers willing and able to respond to disasters: An assessment of tertiary health care system of Khyber Pakhtunkhwa.

For the tertiary health care system to provide adequate care during disasters, willing and able healthcare providers must be available to respond to the abnormal surge of the patients. Health care professionals (HCPs) constantly face a dilemma because of their profession to either respond to disasters or protect themselves. This study was conducted to assess the willingness and ability of HCPs working in the tertiary healthcare system of Khyber Pakhtunkhwa to respond to disasters. This cross-sectional survey was conducted in all the 8 tertiary care hospitals of the Khyber Pakhtunkhwa province of Pakistan. For different disaster scenarios, between 6% and 47% of HCP indicated their unwillingness, and between 3% & 41% of HCPs indicated that they were unable to respond to the given disaster scenarios. HCPs with childcare obligation indicated significantly lower willingness (p<0.05) to respond to earthquakes, MCIs, and an outbreak of Influenza, and SARS. Male HCPs showed a significantly (p<0.05) higher willingness to respond to earthquakes, MCIs, and an outbreak of Influenza as compared to their female counterparts. The overall ability indicated by HCPs for various disaster scenarios ranged between 54.1% [95% CI 0.503,0.578] for responding to victims of nuclear war and 96.4% [95% CI 0.947,0.976] for responding to conventional war. The HCPs who indicated childcare obligation showed a significantly lower ability (p<0.05) to respond to environmental disaster, influenza outbreak, and responding to victims of nuclear war. Female HCPs indicated significantly higher ability (p<0.05) as compared to their male counterparts. This survey provides an opportunity for the tertiary healthcare system to build on the findings and develop disaster mitigation plans to address the barriers to improving the HCPs' availability during disasters.

Reactive oxygen species induced oxidative damage to DNA, lipids, and proteins of antibiotic-resistant bacteria by plant-based silver nanoparticles.

This study assesses the mechanism of action of plant-based silver nanoparticles (AgNPs) against antibiotic-resistant bacteria. We compared AgNPs synthesized through Salvia moorcroftiana and Origanum vulgare extracts and their conjugates with the antibiotic Ceftriaxone for their capacity to cause oxidative damage through reactive oxygen species (ROS). We quantified ROS in the cells of two bacterial strains after treating them with all AgNP types and observed that AgNPs were most effective in K. pneumoniae as they resulted in the highest ChS1 count (44,675), while in P. aeruginosa, Cfx-AgNPs induced the highest levels of ROS with ChS1 count of 56,865. DNA analysis showed that both plant-based AgNPs (O-AgNPs = 0.192 and S-AgNPs = 0.152) were most effective in K. pneumoniae and S-AgNPs (abs = 0.174) and O-Cfx-AgNPs (abs = 0.261) in P. aeruginosa. We observed a significant increase in the levels of conjugated dienes (86.4 µM) and malondialdehyde (172.25 nM) in the bacterial strains after treatment with AgNPs, compared to the control (71.65 µM and 18.064 nM, respectively, in K. pneumoniae and P. aeruginosa). These results indicate lipid peroxidation. AgNPs also increased the levels of protein thiols (0.672 nM) compared to the control (0.441 nM) in K. pneumoniae, except for Chem-AgNPs (0.21 nM). These results suggest that plant-based AgNPs are more effective in oxidizing bacterial DNA, protein, and lipids than Chem-AgNPs. Furthermore, protein oxidation varied between AgNPs alone and AgNPs-antibiotic conjugates. The highest levels of protein thiols were found in the samples treated with O-Cfx-AgNPs (0.672 nM and 0.525 nM in K. pneumoniae and P. aeruginosa, respectively). The results demonstrated that AgNPs kill bacteria by altering bacterial macromolecules such as DNA, lipids, and proteins.

Synthesis of hydrazinylthiazole carboxylates: a mechanistic approach for treatment of diabetes and its complications.

Aim: The deaths of thousands of people and millions affected by diabetes mellitus triggered us to look for alternative possible solutions to cure diabetes and its complications. Materials & methods: A series of hydrazinylthiazole carboxylates (3a-n) was prepared by cyclocondensation reaction of thiosemicarbazones with ethyl 2-chloroacetoacetate. These compounds were screened for antidiabetic potential through α-amylase inhibition, antiglycation and antioxidant assays. Results & conclusion: Most of the compounds exhibited a promising antidiabetic property. Compounds 3e and 3h showed excellent α-amylase and glycation inhibition properties. The hemolytic assay indicated that all compounds are biocompatible. Docking studies carried out on α-amylase target showed correlation between in vitro inhibition and binding energy.

Facile Synthesis and DFT Analysis of Novel Thiazole-Based Hydrazones: An Experimental and Theoretical Perspective.

Hydrazone compounds with remarkable nonlinear optical (NLO) properties were found with vast applications due to their cost-effective synthesis and greater stability. Therefore, we synthesized hydrazone scaffolds (TCAH1-TCAH8) by condensation reaction, and their structural confirmation was accomplished with spectroscopic methods (1H-, 13C-NMR, and HRMS). Quantum chemical calculations were also performed at B3PW91/6-311G(d,p) functional of DFT to explore electronic, structural, and chemical properties. To understand the NLO responses of afore-said chromophores, various kinds of analyses such as natural bonding orbitals (NBOs), frontier molecular orbitals (FMOs), UV-vis analysis, and density of states (DOS) were performed. Findings showed that the HOMO-LUMO energy gap in TCAH8 (3.595 eV) was found to be lower than the TCAH1-TCAH7 (4.123-3.932 eV) with a large red shift which leads to a substantial NLO response. Furthermore, strong intramolecular interactions showed the highest stabilization energy (24.1 kcal mol-1) for TCAH8 in the NBO transitions, combined with the least binding energy. The significant NLO response of TCAH4 was explored with ⟨α⟩, ßtot, and ⟨γ⟩ values as 5.157 × 10-23, and 2.185 × 10-29, and 2.753 × 10-34 esu, respectively, among the entitled compounds. The recent findings may inspire scientists to develop extremely effective NLO materials for forthcoming hi-tech applications.

Quantum Chemical Exploration of A-π1-D1-π2-D2-Type Compounds for the Exploration of Chemical Reactivity, Optoelectronic, and Third-order Nonlinear Optical Properties.

Organic compounds exhibit significant nonlinear optical (NLO) properties and can be utilized in various areas like optical parameters, fiber optics, and optical communication. Herein, a series of chromophores (DBTD1-DBTD6) with an A-π1-D1-π2-D2 framework was derived from a prepared compound (DBTR) by varying the structure of π-spacer and terminal acceptor. The DBTR and its investigated compounds were optimized at the M06/6-311G(d,p) level of theory. Frontier molecular orbitals (FMOs), nonlinear optical (NLO) properties, global reactivity parameters (GRPs), natural bonding orbital (NBO), transition density matrix (TDM), molecular electrostatic potential (MEP), and natural population analysis (NPA) were accomplished at the abovementioned level to describe the NLO findings. DBTD6 has the lowermost band gap (2.131 eV) among all of the derived compounds. The decreasing order of highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap values was DBTR > DBTD1 > DBTD2 > DBTD3 > DBTD4 > DBTD5 > DBTD6. The NBO analysis was carried out to describe noncovalent interactions such as conjugative interactions and electron delocalization. From all of the examined substances, DBTD5 showed the highest λmax value at 593.425 nm (in the gaseous phase) and 630.578 nm (in chloroform solvent). Moreover, the ßtot and ⟨γ⟩ amplitudes of DBTD5 were noticed to be relatively greater at 1.140 × 10-27 and 1.331 × 10-32 esu, respectively. So, these outcomes disclosed that DBTD5 depicted the highest linear and nonlinear properties in comparison to the other designed compounds, which underlines that it could make a significant contribution to hi-tech NLO devices.

Sustainable remediation of dye-contaminated wastewater using novel cross-linked Hex-CCP-co-PPT microspheres.

The presence of dyes in contaminated water poses substantial dangers to the health of both humans and aquatic life. A process called precipitation polymerization was used to create unique cross-linked hexa-chlorocyclotriphosphazene-co-phenolphthalein (Hex-CCP-co-PPT) microspheres for the purpose of this research. Advanced methods such as X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG) were used to characterise these microspheres. In a simulated solution, the performance of Hex-CCP-co-PPTs as a sorbent for removing MB dye was investigated, and the results showed an unprecedentedly high removal rate of 88.4% for MB. Temperature of 25 °C, a Hex-CCP-co-PPTs dose of 40 mg, an MB concentration of 20 ppm, an MB solution volume of 20 mL, a contact time of 40 min, and a pH of 9 were found to be the optimal experimental conditions. According to the results of the kinetic and adsorption analyses, the PSO and Langmuir adsorption models are the best ones to use. These models favour the chemi-sorption nature and mono-layered adsorption of MB in comparison to Hex-CCP-co-PPTs. Importantly, the thermodynamic analysis demonstrated that the process of removing MB by utilizing Hex-CCP-co-PPTs was endothermic and occurred spontaneously. These findings highlight the potential application of Hex-CCP-co-PPT microspheres in Algal Membrane Bioreactors (AMBRs) for the efficient and sustainable removal of dye from wastewater. This would contribute to the protection of ecosystems as well as the public's health.