Quantum Chemical Approach of Hexaammine (NH3)6 complexant with alkali and alkaline earth metals for their potential use as NLO materials.

In this study, nine new electron rich compounds are presented, and their electronic, geometrical, and nonlinear optical (NLO) characteristics have been investigated by using the Density functional theory. The basic design principle of these compounds is placing alkaline earth metal (AEM) inside and alkali metal (AM) outside the hexaammine complexant. The properties of nine newly designed compounds are contrasted with the reference molecule (Hexaammine). The effect of this doping on Hexaamine complexant is explored by different analyses such as electron density distribution map (EDDM), frontier molecular orbitals (FMOs), density of states (DOS) absorption maximum (λmax), hyperpolarizabilities, dipole moment, transition density matrix (TDM). Non-covalent interaction (NCI) study assisted with isosurfaces has been accomplished to explore the vibrational frequencies and types of synergy. The doping of hexaammine complexant with AM and AEM significantly improved its characteristics by reducing values of HOMO-LUMO energy gaps from 10.7eV to 3.15eV compared to 10.7 eV of hexaammine. The polarizability and hyperpolarizability (αo and ßo) values inquisitively increase from 72 to 919 au and 4.31 × 10-31 to 2.00 × 10-27esu respectively. The higher values of hyperpolarizability in comparison to hexaammine (taken as a reference molecule) are credited to the presence of additional electrons. The absorption profile of the newly designed molecules clearly illustrates that they are highly accompanied by higher λmax showing maximum absorbance in red and far-red regions ranging from 654.07 nm to 783.94 nm. These newly designed compounds have superior outcomes having effectiveness for using them as proficient NLO materials and have a gateway for advanced investigation of more stable and highly progressive NLO materials.

Designing Y-shaped two-dimensional (2D) polymer-based donor materials with addition of end group acceptors for organic and perovskite solar cells.

CONTEXT: For the advancement in fields of organic and perovskite solar cells, various techniques of structural alterations are being employed on previously reported chromophores. This way, molecules with all the properties desired for better performance of solar cells can be achieved. In this regard, theoretical modeling of chromophores has gained quite an interest due to its ability to save time, resources, and money. Herein, five new Y-shaped donor materials were theoretically engineered by adding electron-withdrawing acceptors on reported 2DP molecule. The results explored that, in comparison to 2DP, the produced molecules showed red shift in the absorption peaks, smaller bandgaps and binding energies, lower excitation potential, and greater dipole moment and were also highly reactive. When paired with PC61BM, proposed compounds exhibited higher estimated power conversion efficiencies and open-circuit voltage in contrast to 2DP. Individually, 2DP1 possessed the largest conductivity of electrons and the maximum mobility of holes, due to its computed lowest reorganization energies. The results illustrate the viability of the proposed procedure, opening doors for the manufacturing of required solar cells with enhanced photovoltaic properties. METHODS: Precisely, a DFT and TD-DFT analysis on 2DP and all of the proposed molecules was conducted, using the functional MPW1PW91 at 6-31G (d,p) basis set to examine their optoelectronic aspects; additionally, the solvent state computations were studied with a TD-SCF simulation. For all these simulations, Gaussian 09 and GaussView 5.0 were employed. Moreover, the Origin 6.0 software, Multiwfn 3.8 software, and PyMOlyze 1.1 software were utilized for the visual depiction of the graphs of absorption, TDM, and DOS, respectively, of the studied molecules. A number of crucial aspects such as FMOs, bandgaps, light-harvesting efficiency, electrostatic potential, dipole moment, ionization potential, open-circuit voltage, fill factor, binding energy, interaction coefficient, chemical hardness-softness, and electrophilicity index were also investigated for the studied molecules.

Methoxy triphenylamine hexaazatrinaphthylene based small molecules as donor material for photovoltaic applications.

Organic solar cells (OSCs) are capturing huge interest because of their numerous benefits, which include transparency, flexibility, and solution processability. In current project, five new donor molecules (J1-J5) were designed by employing the strategy of end capped alteration of the acceptor moieties on the two sides of the reference molecule. The Methoxy Triphenylamine hexaazatrinaphthylene (MeO-TPA-HATNA) have been used as a reference molecule in this study. DFT and TD-DFT methods employing B3LYP/6-31G (d, p) functional has been applied to perform different analysis. Geometrical, and opto-electronic features of all tailored chromophores were investigated, and comparison was made with the reference J. Among all tailored molecules, J5 shows highest λmax (862 nm) with the least band gap of 1.28 eV. TDM and DOS analysis revealed the high rate of charge transfer. Further, reorganization energy calculations are also executed to examine the charge transfer features of the designed molecules. The results shows that J5 among all these molecules has the highest rate of charge carrier (electron and hole) mobility with least RE values and this molecule can be used as a promising donor material for OSCs with remarkable charge transferring properties. Furthermore, the designed materials showed a suitable HOMO along with higher LUMO energy levels with respect to PC61BM molecule and coupling the PC61BM acceptor with investigated donor molecules gives highly increased Voc (0.66-0.76 V) than reference molecule (0.49 V) and also the power conversion efficiency (PCE) is elevated to 15.09%. The outcomes of current theoretical research have demonstrated that the end capped alteration of different acceptor groups is an excellent strategy to get OSCs with desirable photovoltaic performance. As, all the newly created molecules (J1-J5) have exhibited outstanding electronic and optical properties therefore, these can be expectedly prove excellent material for creating high efficiency future organic photovoltaic devices.

Spatio-temporal change detection of land use and land cover in Malakand Division Khyber Pakhtunkhwa, Pakistan, using remote sensing and geographic information system.

The land use land cover (LULC) change due to the rapidly growing population is a common feature of the urban area. The rapidly growing population in Malakand Division is a greater threat to the LULC of the area due to its negative impact on environment and ecology. This research aims to detect the variations in LULC from 1991 to 2017 in the Malakand Division, Khyber Pakhtunkhwa (KP) province of Pakistan. The study relies on secondary dataset downloaded from the US Geological Survey (1991, 2001, 2011, and 2017 imageries) and the United Nations Office for the Coordination of Humanitarian Affairs (UN OCHA) website. Maximum likelihood technique under supervised image classification was opted to analyze the LULC changes in between 1991 and 2017. The results were based on six major land use classes including agriculture built-up area, vegetation cover, water bodies, snow cover, and barren land. The results from 1991 to 2017 show a substantial reduction in snow cover and barren land which is consequence of climate change. A known change has been recorded in built-up area which shows an increase from 1.02 to 6.2% with a change of 5.18% of the total land. The vegetation cover water bodies were also showing increase in area. The vegetation cover increased from 28.89 to 44.67% while barren land decreased from 45.68 to 40.29% of the total area. Furthermore, the built-up area increased from 1.02 to 6.2%, whereas water covers increased from 0.63% (1991) to 0.86% (2017) of the total area. The study concludes that there is an immense need for planning to preserve the natural habitat for sustainable development in the area.

Alkaline earth metals (Be, Mg, Ca) doped hexamine complexant with enhanced electronic and nonlinear optical properties.

Organic complexant hexamine (hexamethylenetetramine, HMTA) is doped with alkaline earth (AE) metals, and new complexes are designed systematically to explore their nonlinear optical (NLO) properties by carrying out DFT calculations. Optimization of afresh designed geometries has shown their sufficient thermodynamic stability. Moreover, the energy band gap of pure HMTA is 10.62 eV which is reduced up to 2.63 eV for our doped complexes. This shows that alkaline earth metals are effective in enhancing the electronic properties of a system. Time-dependent DFT calculations are achieved, and results show that higher absorption maxima (λmax) along with small transition energies (ΔE) have significantly increased the hyperpolarizability (ß0) values (21,338-220,585 au). This higher hyperpolarizability is an elementary prerequisite for improved NLO response of a material. Transition density matrix (TDM) analysis, density of states (DOS) analysis, and electron density difference map (EDDM) studies are executed to get information about electronic distribution, crucial transitions, and electron transfer properties. As a result of these findings, it can be concluded that alkaline earth metal-doped HMTA might be a competitor for NLO materials with remarkable optical and electronic properties and better future applications in the field of optoelectronics.

Designing neodymium-doped hexamine complexant as novel IR NLO material with extremely large non-linear optical behavior.

A new complex named HMNd has been basically designed by doping rare-earth neodymium metal inside the hexamine surface HM. Density functional theory (DFT) calculations were carried out using B3LYP functional with split basis set GENECP to examine their geometrical, electronic, and non-linear optical properties of newly designed complex HMNd. After getting stable geometry of HMNd, its optoelectronic properties were compared with pure HM surface to check the influence of doping. HMNd revealed the obvious reduction in band gap energies from 8.4 eV (HM) to 1.79 eV (HMNd) as confirmed through DOS analysis. The highest hyperpolarizability and linear isotropic polarizability values of 6.8 × 105 a.u and 262.81 a.u respectively are perceived in HMNd. Electronic and thermodynamic stability of the designed complex has been confirmed through their vertical ionization and interaction energies. As revealed through the UV-visible analysis, doping with neodymium metal (HMNd) shifts the absorption to IR region with λmax of 2699.63 nm which leads towards the production of new materials. These upshots highlight the adequacy of designed complex providing gateway for designing new IR NLO materials in laser frequency conversion technology having usages in versatile fields.

Carbazole-based donor materials with enhanced photovoltaic parameters for organic solar cells and hole-transport materials for efficient perovskite solar cells.

Five carbazole-based donor molecules are designed by structural engineering of reference molecule PF. The molecules are devised by substitution of thiophene bridged end-capped acceptor groups namely (2-methylenemalononitrile) PF1, (methyl 2-cyanoacrylate) PF2, (3-methyl-5-methylene-2-thioxothiazolidin-4-one) PF3, (2-(3-methyl-5-methylene-4-oxothiazolidin-2- ylidene) malononitrile) PF4, and (4-(5-methylthiophen-2-yl) benzo[c] [1, 2, 5] thiadiazol) PF5. A DFT investigation was performed at the selected DFT functional MPW1PW91/6-31G (d,p) to investigate the optoelectronic properties of PF and all designed (PF1-PF2) molecules. Several important characteristics, i.e., band gap (Eg), transition density matrix analysis, dipole moment (µ), density of states analysis, reorganization energies, open circuit voltage (Voc), and fill factor, were investigated. The comparison of energy levels of reference molecule and designed molecules unveils the fact that these molecules are efficient hole transport materials to be used in perovskite solar cells (PSCs). All the newly drafted molecules (PF1-PF5) show higher λmax values in solvent (Chlorobenzene) ranging from 529 to 614 nm than the reference PF (344 nm). Smaller band gap (Eg) values in a range of 2.27-1.9 eV for newly designed molecules are observed which are very much reduced when compared to reference PF. Lowered exciton binding energies (Eb) and reorganization energies for the electron (0.004279-0.0103337 eV) as compared to PF reveal that our molecules display higher electron mobility rates, and hence, these small molecules can be used as proficient donor materials in high-performance organic solar cells (OSCs) and better hole transport materials (HTMs) for possible application in perovskite solar cells.

Epigallocatechin gallate: Phytochemistry, bioavailability, utilization challenges, and strategies.

Epigallocatechin gallate (EGCG), a green tea catechin, has gained the attention of current study due to its excellent health-promoting effects. It possesses anti-obesity, antimicrobial, anticancer, anti-inflammatory activities, and is under extensive investigation in functional foods for improvement. It is susceptible to lower stability, lesser bioavailability, and lower absorption rate due to various environmental, processing, formulations, and gastrointestinal conditions of the human body. Therefore, it is the foremost concern for the researchers to enhance its bioactivity and make it the most suitable therapeutic compound for its clinical applications. In the current review, factors affecting the bioavailability of EGCG and the possible strategies to overcome these issues are reviewed and discussed. This review summarizes structural modifications and delivery through nanoparticle-based approaches including nano-emulsions, encapsulations, and silica-based nanoparticles for effective use of EGCG in functional foods. Moreover, recent advances to enhance EGCG therapeutic efficacy by specifically targeting its molecules to increase its bioavailability and stability are also described. PRACTICAL APPLICATIONS: The main green tea constituent EGCG possesses several health-promoting effects making EGCG a potential therapeutic compound to cure ailments. However, its low stability and bioavailability render its uses in many disorders. Synthesizing EGCG prodrugs by structural modifications helps against its low bioavailability and stability by overcoming premature degradation and lower absorption rate. This review paper summarizes various strategies that benefit EGCG under different physiological conditions. The esterification, nanoparticle approaches, silica-based EGCG-NPs, and EGCG formulations serve as ideal EGCG modification strategies to deliver superior concentrations with lesser toxicity for its efficient penetration and absorption across cells both in vitro and in vivo. As a result of EGCG modifications, its bioactivities would be highly improved at lower doses. The protected or modified EGCG molecule would have enhanced potential effects and stability that would contribute to the clinical applications and expand its use in various food and cosmetic industries.

Women's participation in disaster recovery after the 2005 Kashmir, Pakistan earthquake.

This study sought to learn how women participated in the recovery process after the Kashmir earthquake of October 2005 in Union Council Langarpura, Azad Kashmir state of Pakistan. Focus-group discussions, semi-structured interviews, and participant observations were conducted with a total of 48 participants. The results revealed that women played various important roles in the reproductive, productive, and community spheres, encompassing, inter alia, normal household responsibilities of cooking, cleaning, and caring for cattle, and non-traditional tasks such as rebuilding the home. In addition, they participated in income-generating activities such as carrying construction materials and water for daily wages, dairy farming, and working in fields and in the education and health sectors. Community endeavours, meanwhile, consisted of search and rescue, caring for the injured, collective cooking and food sharing, and supervising the reconstruction of public structures, including schools, roads, and water supply facilities, and establishing a sewing centre to provide vocational training to local women.

A randomized control trial comparing the effects of motor relearning programme and mirror therapy for improving upper limb motor functions in stroke patients.

OBJECTIVE: To compare the effectiveness of motor relearning programme with mirror therapy in upper limb motor functions of stroke patients. METHODS: The randomised control trial was conducted in Rafsan Neuro Rehabilitation Centre, Peshawar, Pakistan, from June to December 2017, and comprised stroke patients who had Mini Mental State Examination score over 24. Participants were randomly allocated into treatment and control groups. The treatment group underwent a Motor Relearning Programme, while the control group received Mirror therapy. Upper limb sub-scales of the motor assessment scale were used as data collection tool. SPSS 20 was used for data analysis. RESULTS: Of the 66 subjects, 46(69.7%) were males and 20(30.3%) were females. The overall mean age was 55.44±9.21 years. Left hemiplegia was found in 31(47%) subjects, while 35(53%) had right hemiplegia. Each of the two groups had 33(50%) subjects. There were significant differences between pre-treatment and post-treatment mean scores of upper arm functions, hand function and advance hand activities of the two groups (p<0.05 each). All the three variables significantly improved in the treatment group compared to the control group (p<0.001). CONCLUSIONS: Motor Relearning Programme and Mirror therapy were found to be effective in improving upper limb motor functions of stroke patients, but the former was found to be more effective than the latter.

ANTIOXIDANTS AND ANTIFUNGAL ACTIVITIES OF SUBSTITUTED GUANIDINES AND THEIR COPPER COMPLEXES.

A series of guanidines and their copper (II) complexes were investigated for their radical scavenging activity including peroxyl radicals (ROO), superoxide anion (O2), hydroxyl ('OH), and reactive hydrogen per- oxide (H202) species. Among the Cu(II) complexes, Cu-MR-9-2 shows the highest, Cu-MR-9-3, Cu-MR-9-6 less and Cu-MR-9-1 least antioxidant potential. The Cu(II) complexes show better Fea'-chelating activity than that of ligands. Among the Cu(II) complexes Cu-MR-9-2 was found to have the highest, Cu-MR-9-6 moderate, MR-9-3 less and Cu-MR-9-1 least ferric reducing capacity. The IC50 values for ligands (MR-9-1, MR-9-2, MR- 9-3, MR-9-6) were determined to be 197.53 ± 7.13, 189.07 ± 7.34, 207.98 ± 6.78 and 233.38 ±6.37 pM, which showed lower antioxidant activity than their Cu(II) complexes. The IC,o values for ascorbic acid were found to be 51.60 ± 13.18 pM. The Cu(I) metal compounds (Cu-MR-9-1,Cu-MR-9-2, Cu-MR-9-3 and Cu-MR-9-6) were detected to be the most powerful scavengers of the hydroxyl radical with IC50 up to 108.03 ± 11.34 pM, 101.41 ±12.10 pM, 90.59 ± 11.53 pM and 88.86 ± 13.16 pM, respectively.