Charge transfer in TiO2-based photocatalysis: fundamental mechanisms to material strategies.

Semiconductor-based photocatalysis has attracted significant interest due to its capacity to directly exploit solar energy and generate solar fuels, including water splitting, CO2 reduction, pollutant degradation, and bacterial inactivation. However, achieving the maximum efficiency in photocatalytic processes remains a challenge owing to the speedy recombination of electron-hole pairs and the limited use of light. Therefore, significant endeavours have been devoted to addressing these issues. Specifically, well-designed heterojunction photocatalysts have been demonstrated to exhibit enhanced photocatalytic activity through the physical distancing of electron-hole pairs generated during the photocatalytic process. In this review, we provide a systematic discussion ranging from fundamental mechanisms to material strategies, focusing on TiO2-based heterojunction photocatalysts. Current efforts are focused on developing heterojunction photocatalysts based on TiO2 for a variety of photocatalytic applications, and these projects are explained and assessed. Finally, we offer a concise summary of the main insights and challenges in the utilization of TiO2-based heterojunction photocatalysts for photocatalysis. We expect that this review will serve as a valuable resource to improve the efficiency of TiO2-based heterojunctions for energy generation and environmental remediation.

Thiadiazine thione derivatives as anti-leishmanial agents: synthesis, biological evaluation, structure activity relationship, ADMET, molecular docking and molecular dynamics simulation studies.

During last decades, 3,5-disubstituted-tetrahydro-2H-thiadiazine-2-thione scaffold remains the center of interest due to their ease of preparation, diverse range substituents at N-3 and N-5 positions, and profound biological activities. In the current study, a series of 3,5-disubstituted-tetrahydro-2H-thiadiazine-2-thiones were synthesized in good to excellent yield, and the structure of the compounds were confirmed by various spectroscopic techniques such as FTIR, 1H-NMR, 13C-NMR and Mass spectrometry, and finally evaluated against Leishmania major. Whereas, all the evaluated compounds (1-33), demonstrate potential leishmanicidal activities with IC50 values in the range of (1.30- 149.98 uM). Among the evaluated compounds such as 3, 4, 6, and 10 exhibited excellent leishmanicidal activities with IC50 values of (2.17 µM), (2.39 µM), (2.00 µM), and (1.39 µM), respectively even better than the standard amphotericin B (IC50 = 0.50) and pentamidine (IC50 = 7.52). In order to investigate binding interaction of the most active compounds, molecular docking study was conducted with Leishmania major. Further molecular dynamic simulation study was also carried out to assess the stability and correct binding of the most active compound 10, within active site of the Leishamania major. Likewise, the physiochemical properties, drug likeness, and ADMET of the most active compounds were investigated, it was found that none of the compounds violate Lipiniski's rule of five, which show that this class of compounds had enough potential to be used as drug candidate in near future.Communicated by Ramaswamy H. Sarma.

First Report on Microplastics Quantification in Poultry Chicken and Potential Human Health Risks in Pakistan.

Microplastics (MPs) are an emerging environmental health concern due to their widespread occurrence in food sources such as fish, meat, chicken, honey, sugar, salt, tea and drinking water, thereby posing possible risks to human health. This study aimed to observe the existence of MPs in the crop and gizzard of the farm chicken, a significant food source in Pakistan. Twenty-four chicken samples were taken from eight poultry farms across Punjab, Pakistan. A total of 1227 MP particles were found from 24 samples (crop and gizzards) originating from the 8 poultry farms. In all, 429 MP particles were found in 24 chicken crops, with a mean of 17.8 ± 12.1 MPs/crop. In contrast, 798 MP particles were found in 24 chicken gizzards, with a mean of 33.25 ± 17.8 MPs/gizzard. Comparatively larger particles, ranging between 300-500 µm, were more abundant (63%) than other considered sizes (300-150 µm [21%] and 150-50 µm [16%]). Additionally, fragments were the dominant type of shape in both sample types (crop [64%] and gizzard [53%]). The predominant colours of particles extracted from gizzards and crops were yellow (32%) and red (32%), respectively. Chemical characterisation of these particles detected four types of polymers: polyvinyl chloride (PVC) at 51.2%, followed by low-density polyethylene (LDPE) at 30.7%, polystyrene (PS) at 13.6% and polypropylene homopolymer (PPH) at 4.5%. In conclusion, we provide evidence for MPs in the gizzards and crops of farmed chickens which may originate from contaminated poultry feed. Only a few studies have been reported globally to assess MPs ingestion in chickens. The current study is the first report from Pakistan. It could be a valuable addition to support MPs literature to establish a relationship between MPs contamination and intake through the food chain.

Dihydropyrazole Derivatives Act as Potent α-Amylase Inhibitors and Free Radical Scavengers: Synthesis, Bioactivity Evaluation, Structure-Activity Relationship, ADMET, and Molecular Docking Studies.

Dihydropyrazole (1-22) derivatives were synthesized from already synthesized chalcones. The structures of all of the synthesized compounds were confirmed by elemental analysis and various spectroscopic techniques. Furthermore, the synthesized compounds were screened against α amylase as well as investigated for antioxidant activities. The synthesized compounds demonstrate good to excellent antioxidant activities with IC50 values ranging between 30.03 and 913.58 µM. Among the 22 evaluated compounds, 11 compounds exhibit excellent activity relative to the standard ascorbic acid IC50 = 287.30 µM. Interestingly, all of the evaluated compounds show good to excellent α amylase activity with IC50 values lying in the range between 0.5509 and 810.73 µM as compared to the standard acarbose IC50 = 73.12 µM. Among the investigated compounds, five compounds demonstrate better activity compared to the standard. In order to investigate the binding interactions of the evaluated compounds with amylase protein, molecular docking studies were conducted, which show an excellent docking score as compared to the standard. Furthermore, the physiochemical properties, drug likeness, and ADMET were investigated, and it was found that none of the compounds violate Lipiniski's rule of five, which shows that this class of compounds has enough potential to be used as a drug candidate in the near future.

Thiophene-Derived Schiff Base Complexes: Synthesis, Characterization, Antimicrobial Properties, and Molecular Docking.

Novel thiophene-derived Schiff base ligand DE, where DE is (E)-N1,N1-diethyl-N2-(thiophen-2-ylmethylene)ethane-1,2-diamine, and the corresponding M(II) complexes, [M(DE)X2] (M = Cu or Zn, X = Cl; M = Cd, X = Br), were prepared and structurally characterized. X-ray diffraction studies revealed that the geometry around the center of the M(II) complexes, [Zn(DE)Cl2] and [Cd(DE)Br2], could be best described as a distorted tetrahedral. In vitro antimicrobial screening of DE and its corresponding M(II) complexes, [M(DE)X2], was performed. The complexes were more potent and showed higher activities against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa, fungi Candida albicans, and protozoa Leishmania major compared to the ligand. Among the studied complexes, [Cd(DE)Br2] exhibited the most promising antimicrobial activity against all the tested microbes compared to its analogs. These results were further supported by molecular docking studies. We believe that these complexes may significantly contribute to the efficient designing of metal-derived agents to treat microbial infections.

Biosynthesis and Characterization of Silver Nanoparticles Using Tribulus terrestris Seeds: Revealed Promising Antidiabetic Potentials.

Green synthesis is the most effective and environmentally friendly way to produce nanoparticles. The present research aimed at the biosynthesizing of silver nanoparticles (AgNPs) using Tribulus terrestris seed extract as the reducing and stabilizing agent and investigating their anti-diabetic properties. Fourier transformation infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis spectroscopy were used to analyze the synthesized silver nanoparticles from Tribulus terrestris (TT-AgNPs). The spectroscopic characterization revealed a surface Plasmon resonance band at 380 nm, which verified the development of TT-AgNPs. The transmittance peaks were observed at 596, 1450, 1631, 2856, 2921, and 3422 cm-1 through the FTIR spectrophotometer. The XRD spectrum showed four distinct diffraction peaks in the 2θ range at 20° to 60°. Intense peaks were at 26.32°, 30.70°, 44.70°, 56.07°, 53.75°, 66.28°, and 75.32°. The SEM analysis revealed that the prepared TT-AgNPs were clustered loosely with a smooth and spherical structure and were of relatively uniform size. The in vitro antidiabetic potential of TT-AgNPs was assessed by using glucose yeast uptake, glucose adsorption, and alpha-amylase assays. TT-AgNPs showed the highest activity (78.45 ± 0.84%) of glucose uptake by yeast at 80 µg/mL. In the glucose adsorption assay, the highest activity of TT-AgNPs was 10.40 ± 0.52% at 30 mM, while in the alpha-amylase assay, TT-AgNPs exhibited the maximum activity of 75.68 ± 0.11% at 100 µg/mL. The results indicate a substantial anti-diabetic effect of the TT-AgNPs. Furthermore, the in vivo antidiabetic study was performed on TT-AgNPs in streptozotocin-induced diabetic mice. After receiving TT-AgNPs treatment for 30 days, the mice were sacrificed for biochemical and histological analyses of pancreatic and liver samples, which demonstrated a good improvement when compared to the control group. Mice treated with TT-AgNPs showed a significant drop in blood sugar levels, showing that the biosynthesized TT-AgNPs have effective anti-diabetic properties.

Biosynthesis and Anti-inflammatory Activity of Zinc Oxide Nanoparticles Using Leaf Extract of Senecio chrysanthemoides.

Nanotechnology has recently appeared as an important study subject in modern material sciences. Greener synthesis of nanoparticles has gained the attention of many scientists because of its integral characteristics such as effectiveness, eco-friendly, and low cost. In the present study by following the green synthesis approach, zinc oxide nanoparticles (ZnO NPs) were formed for the very first time by using Senecio chrysanthemoides leaf extract as a reducing agent. The UV-Vis spectrophotometer was used to study the synthesized ZnO NPs, and the specific peak was found to be at 349 nm. The characteristic Fourier transform infrared (FTIR) peak was found to be at 449 cm-1 which displays the peak of ZnO molecules. The surface morphology of the ZnO NPs was determined via scanning electron microscopy (SEM). The energy-dispersive X-ray spectroscopy (EDX) study showed that the synthesized ZnO NPs are present at the weight percentage of 66.38%. The X-ray diffraction (XRD) spectrum confirmed the hexagonal phase wurtzite structure, with the average particle size of 31 nm, and demonstrated the crystalline structure of ZnO NPs. Additionally, to all these experiments, we compared the anti-inflammatory properties of biogenic ZnO NPs to a standard drug. Biosynthesized ZnO NPs have revealed an effective anti-inflammatory activity at a higher concentration (100 mL-1) and showed 73% inhibition in comparison with diclofenac sodium drug. Zinc oxide was shown to be compatible with diclofenac sodium, according to the results. The ZnO NPs produced using the greener synthesis process have the potential to be used in a broad range of fields and also used as a good anti-inflammatory agent.

Evaluating groundwater nitrate and other physicochemical parameters of the arid and semi-arid district of DI Khan by multivariate statistical analysis.

Nitrate as an important water pollutant, causing eutrophication was analyzed in Pakistan at different water sources (hand pump (HP), bore hole (BH) and tube well (TW)) to assess the contamination level caused by NO3-. NO3- concentrations in the HP water samples were 31 mg L-1 to 59 mg L-1, in BH 20 mg L-1 to 79 mg L-1 while in TW water samples it was between 29 to 55 mg L-1. The association of NO3- with other selected parameter in groundwater can be determined by using statistical approaches. Different physicochemical parameters (pH, electrical conductivity (EC), temperature and dissolved oxygen (DO)) were studied in groundwater samples of the research district. The Pearson correlation coefficient (r) for groundwater characteristics were calculated. Hierarchical Cluster Analysis (HCA) was used to categorize samples based on their groundwater quality similarities and to find links between groundwater quality factors. The key relationship of the groundwater for HP samples on EC and TDS (r = 1) had a great correlation, while all other parameters correlations were lower (r = 0.40), BH's parameters on WT and WSD (r = 0.57), WT and pH (r = 0.57), EC and DO (r = 0.50), DO and TDS (0.50), EC and TDS (r = 1) had a quite high correlation, while all other parameters correlations were less than (r = 0.40), on the other hand, tube well parameters on TDS and EC (r = 1) had a perfect correlation, DO and pH (r = 0.75) parameters correlations were less than (r = 0.40).

Synthetic Transformation of 2-{2-Fluoro[1,1'-biphenyl]-4-yl} Propanoic Acid into Hydrazide-Hydrazone Derivatives: In Vitro Urease Inhibition and In Silico Study.

In the present study, 28 acyl hydrazones (4-31) of flurbiprofen were synthesized in good to excellent yield by reacting different aromatic aldehydes with the commercially available drug flurbiprofen. The compounds were deduced with the help of different spectroscopic techniques like 1H-NMR and HREI-MS and finally evaluated for in vitro urease inhibitory activity. All of the synthesized products demonstrated good inhibitory activities in the range of IC50 = 18.92 ± 0.61 to 90.75 ± 7.71 µM as compared to standard thiourea (IC50 = 21.14 ± 0.42 µM). Compound 30 was found to be the most active among the series better than the standard thiourea. A structure-activity relationship (SAR) study revealed that the presence of electron-donating groups on the phenyl ring plays a prominent role in the inhibition of the urease enzyme. Moreover, in silico molecular modeling analysis was carried out to study the effect of substituents in synthesized derivatives on the binding interactions with the urease enzyme.

Effect of dietary supplementation of Neem, Azadirachta indica leaf extracts on enhancing the growth performance, chemical composition and survival of rainbow trout, Oncorhynchus mykiss.

Rainbow trout Oncorhynchus mykiss has a great nutritional value and delicious taste. A 90-days experimental trial was conducted to investigate the effect of dietary leaf extract of neem tree Azadirachta indica as a feeding supplement on the growth performance and proximate composition of O. mykiss. Four experimental diets were designed as T1 (with 5% A. indica leaf extract), T2 (with 7% of A. indica leaf extract), T3 (with 10% A. indica leaf extract), and T4 (control group feed with a regular diet with 0% A. indica leaf extract). The average initial weight of fry 0.4 ± 0.14 g was stocked at 25 fish/tank with two replicates per treatment (4 × 2 = 8). After 90 days of the experimental trial, One-way ANOVA showed significant differences in final body weight, weight gain, specific growth rate, feed conversion ratio, and survival rate among the treatment groups (p < 0.05). The highest final body weight (48.10 g) and weight gain (47.70 g) was observed in T2 with 7% A. indica leaf extract, which was significantly different from the other treatments (p < 0.05). The lowest FCR was recorded in T2 (1.90), which was significantly different compared to other treatment groups (p < 0.05). Inclusion of A. indica leaf extract in formulated feed for rainbow trout had significant effects in the hepatosomatic index, viscerosomatic index and Fulton's condition factor (p < 0.05), but there was no significant difference in the survival rate of rainbow trout fry treated with different experimental diets (p > 0.05). The phenomenal regression indicates that 7.5% A. indica inclusion is optimum for best growth performance for rainbow trout under a controlled environment. Thus, the present study suggests that the dietary leaf extract has performed an excellent nutritional supplement by enhancing growth performance and health conditions of rainbow trout in the hatchery conditions.

Effect of feeding frequency as a rearing system on biological performance, survival, body chemical composition and economic efficiency of Asian seabass Lates calcarifer (Bloch, 1790) reared under controlled environmental conditions.

A 70-day rearing trial was done to determine the optimal frequency of feeding on growth performance (GP), feed conversion rate (FCR), cannibalism, survival rate (SR), body chemical composition and economic efficiency of the Asian sea bass. This study tested four different treatments of feeding frequencies (FF), once (T1), twice (T2), three times (T3), and four times (T4) per day. An average initial weight of Asian sea bass fry was 0.2 g (SD = ±0.12) were stocked 10 individuals per m3 (9.14 m × 1.82 m × 1.22 m, L × W × H; water depth 0.61 m) with two replicates per treatment (4 × 2 = 8). Fry were fed a mixture of larval commercial feed and shrimp with a pellet diet containing (46% CP). Initially, the feeding rate of 8% biomass per day was further adjusted according to fish biomass on a weekly basis. Results showed that, the FF significantly affected (p < 0.05) on growth indictors and survival rate (SR). Specifically fry fed three times a day (T3) had the best FBW, FL, SGR, ADWG and FCR followed by T4 and T2 while fry fed one time a day was the lowest in these parameters. Also, VSI, HSI and CF (k) significantly differed among the treatments. The fish whole body content of protein, moisture and ash did not significantly (p < 0.05) be affected by feeding frequency, but lipid content differed and both T3, T4 were the highest. It could be concluded that, increasing FF up to three times a day had a positive effect on weight gain, survival rate and feed utilization of Lates calcarifer. The second degree polynomial regression indicates that fed three times a day is optimum for best growth performance and survival for Asian sea bass.

Assessing the physico-chemical parameters and some metals of underground water and associated soil in the arid and semiarid regions of Tank District, Khyber Pakhtunkhwa, Pakistan.

Good-quality water and food are the basic needs of humans, plants, and animals. Polluted groundwater and soil directly and indirectly affect organisms, which is the main environmental concern. In the current study, standard protocols of atomic absorption spectrometry were adopted for the investigation of selected metals (lead, chromium, and iron) in the collected groundwater and soil samples. The Pearson correlation coefficient (r) applied to groundwater and soil samples shows a positive perfect correlation among water parameters (conductivity and total dissolved solids) in all three sources. In the hand pump samples between water table (WT) and water source depth (WSD), Pearson correlation coefficient (r) value was found (r = 0.87) while between EC and TDS, it was r = 1. Similarly, in the bore hole samples between WT and WSD (r = 0.66), EC and TDS (r = 1), EC and Cr (r = 0.70), and TDS and Cr (r = 0.70), which showed weaker correlation. In the tube well samples, correlation between EC and TDS was high (r = 1). The correlation coefficient (r) values of the soil parameters in the hand pump (soil) samples between Fe and Cr (r = 0.86), in bore hole samples between Fe and Cr (r = 0.77), in tube well samples between Fe and Cr (r = 0.69), while all the other parameter correlations were found lower (r = 0.60). Between electrical conductivity and total dissolved solids, high relation has been observed between them (r = 1). Overall, results showed that in most of the studied samples, contents of the target metals were found above the allowable limit set by the World Health Organization (WHO) and the United States Environmental Protection Agency (USEPA).

Selected Thiadiazine-Thione Derivatives Attenuate Neuroinflammation in Chronic Constriction Injury Induced Neuropathy.

Neuropathic pain refers to a lesion or disease of peripheral and/or central somatosensory neurons and is an important body response to actual or potential nerve damage. We investigated the therapeutic potential of two thiadiazine-thione [TDT] derivatives, 2-(5-propyl-6-thioxo-1, 3, 5-thiadiazinan-3-yl) acetic acid [TDT1] and 2-(5-propyl-2-thioxo-1, 3, 5-thiadiazinan-3-yl) acetic acid [TDT2] against CCI (chronic constriction injury)-induced neuroinflammation and neuropathic pain. Mice were used for assessment of acute toxicity of TDT derivatives and no major toxic/bizarre responses were observed. Anti-inflammatory activity was assessed using the carrageenan test, and both TDT1 and TDT2 significantly reduced carrageenan-induced inflammation. We also used rats for the induction of CCI and performed allodynia and hyperalgesia-related behavioral tests followed by biochemical and morphological analysis using RT-qPCR, immunoblotting, immunohistochemistry and immunofluorescence. Our findings revealed that CCI induced clear-cut allodynia and hyperalgesia which was reversed by TDT1 and TDT2. To determine the function of TDT1 and TDT2 in glia-mediated neuroinflammation, Iba1 mRNA and protein levels were measured in spinal cord tissue sections from various experimental groups. Interestingly, TDT1 and TDT2 substantially reduced the mRNA expression and protein level of Iba1, implying that TDT1 and TDT2 may mitigate CCI-induced astrogliosis. In silico molecular docking studies predicted that both compounds had an effective binding affinity for TNF-α and COX-2. The compounds interactions with the proteins were dominated by both hydrogen bonding and van der Waals interactions. Overall, these results suggest that TDT1 and TDT2 exert their neuroprotective and analgesic potentials by ameliorating CCI-induced allodynia, hyperalgesia, neuroinflammation and neuronal degeneration in a dose-dependent manner.

Acute oral toxicity and antioxidant studies of an amine-based diselenide.

BACKGROUND: Organochalcogen compounds have attracted the interest of a multitude of studies for their promising Pharmacological and biological activities. The antioxidant activity and acute toxicity of an organoselenium compound, 1-(2-(2-(2-(1-aminoethyl)phenyl)diselanyl)phenyl)ethanamine (APDP) was determined in mice. METHODS: Mice were randomly divided into four groups, with each group comprising of seven animals. Canola oil (1ml/kg of body weight) was administered to 1st group, while 2nd, 3rd & 4th groups were administered with 10 mg/kg, 30 mg/kg & 350 mg/kg of APDP respectively. APDP was administered by Intragastric gavage as a single oral dose. RESULTS: The APDP oral administration was found to be safe up to 350 mg/kg of body weight and no deaths of animals were recorded. The lethal dose 50 (LD50) for APDP was determined at 72 h and was estimated to be > 350 mg/kg. After acute treatment, all mice were sacrificed by decapitation to determine the antioxidant enzymes and lipid peroxidation values for the treated mice liver. No fluctuation in lipid peroxidation, vitamin C and non protein thiol (NPSH) levels was observed due to the administration of APDP. hepatic α-ALA-D activity, catalase (CAT), superoxide dismutase (SOD) and the biochemical parameters were evaluated. Experimental observation demonstrated that APDP protected Fe(II) induced thiobarbituric acid reactive substances (TBARS) production in liver homogenate significantly (p < 0.05). The administration of APDP (an amine-based diselenide) both in vitro and in vivo clearly demonstrated that this potential compound has no acute toxicity towards mice among all the tested parameter. CONCLUSION: On the basis of experimental results, it is concluded that APDP is a potential candidate as an antioxidant compound for studying pharmacological properties.

Pharmacological mechanisms underlying gastroprotective activities of binapthyl diselenide in Wistar rats.

Selenium (Se) is a dietary essential trace element with important biological roles. It is a nutrient related to the complex metabolic and enzymatic functions. Organoselenium compounds have been reported to have anti-ulcer activity and used as drug for the treatment of gastrointestinal disorders. The antiulcer activity of binapthyl diselenide (NapSe)2 was investigated in ethanol-induced gastric lesions in rats. A number of markers of oxidative stress were examined in rats stomach including thiobarbituric acid reactive species (TBARS), catalase (CAT), superoxide dismutase (SOD), non-protein thiol groups (NPSH) and ascorbic acid. (NapSe)2 was found to be significantly restoring the deficits in the antioxidant defense mechanisms (CAT, SOD, NPSH and ascorbic acid), and suppressed lipid peroxidation in rat stomach resulting from EtOH administration. It is experimentally concluded that ethanol exposure causes alterations in the antioxidant defense system and induces oxidative stress in rat stomach. These studies establish a promising foundation for investigating and understanding the beneficial effects of organoselenium compounds on human health. Moreover, (NaPSe)2 deserves further investigation as a therapeutic and preventive agent against gastric ulcer in humans.

3-Benzyl-5-butyl-1,3,5-thia-diazinane-2-thione.

In the title compound, C(14)H(20)N(2)S(2), the 1,3,5-thia-diazinane-2-thione ring adopts an envelope conformation. The S=C bond length is 1.6776 (15) Å, whereas the S-C bond lengths are 1.7470 (15) and 1.8479 (17) Å. The intramolecular C-H⋯S hydrogen bond between the thione and the benzyl units along with the C-H⋯π interaction between the butyl group and the centroid of the benzene ring may be effective in stabilizing the molecule.

2-[6-Thioxo-5-(2,4,6-trimethyl-phen-yl)-1,3,5-thia-diazinan-3-yl]acetic acid.

In the mol-ecule of the title compound, C(14)H(18)N(2)O(2)S(2), the 1,3,5-thia-diazinane-2-thione ring adopts an envelope conformation with one of the N atoms at the flap position. The plane throught the five co-planar atoms of the heterocycle is oriented at a dihedral angle of 80.59 (8)° with respect to the aromatic ring. In the crystal structure, weak inter-molecular O-H⋯S inter-actions link the mol-ecules into chains along the b axis.