LUMO Research Articles

Exploring the inhibitory action of betulinic acid on key digestive enzymes linked to diabetes via in vitro and computational models: approaches to anti-diabetic mechanisms

ABSTRACT Phytochemicals are now increasingly exploited as remedial agents for the management of diabetes due to side effects attributable to commercial antidiabetic agents. This study investigated the structural and molecular mechanisms by which betulinic acid exhibits its antidiabetic effect via in vitro and computational techniques. In vitro antidiabetic potential was analysed via on α-amylase, α-glucosidase, pancreatic lipase and α-chymotrypsin inhibitory assays. Its structural and molecular inhibitory mechanisms were investigated using Density Functional Theory (DFT) analysis, molecular docking and molecular dynamics (MD) simulation. Betulinic acid significantly (p < 0.05) inhibited α-amylase, α-glucosidase, pancreatic lipase and α-chymotrypsin enzymes with IC50 of 70.02 μg/mL, 0.27 μg/mL, 1.70 μg/mL and 8.44 μg/mL, respectively. According to DFT studies, betulinic acid possesses similar reaction in gaseous phase and water due to close values observed for highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO) and the chemical descriptors. The dipole moment indicates that betulinic acid has high polarity. Molecular electrostatic potential surface revealed the electrophilic and nucleophilic attack-prone atoms of the molecule. Molecular dynamic studies revealed a stable complex between betulinic acid and α-amylase, α-glucosidase, pancreatic lipase and α-chymotrypsin. The study elucidated the potent antidiabetic properties of betulinic acid by revealing its conformational inhibitory mode of action on enzymes involved in the onset of diabetes.

First-Principles Study of Discharge Products and Their Stability for Lithium-Nitrogen Batteries

Li-N2 batteries present a relatively novel approach to N2 immobilization, and an advanced N2/Li3N cycling method is introduced in this study. The low operating overpotential of metal–air batteries is quite favorable to their stable cycling performance, providing a prospect for the development of a new type of battery with extreme voltage. The battery system of Li-N2 uses N2 as the positive electrode, lithium metal as the negative electrode, and a conductive medium containing soluble lithium salts as the electrolyte. In accordance with its voltage-distribution trend, a variety of lithium-nitrogen molecule intermediates are produced during the discharge process. There is a lack of theoretical description of material changes at the microscopic level during the discharge process. In this paper, the first-principles approach is used to simulate and analyze possible material changes during the discharge process of Li-N2 batteries. The discharge process is simulated on a 4N-graphene anode substrate model, and simulations of its electrostatic potential, Density of States (DOS), HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) aspects confirm that the experimentally found Li3N becomes the final stabilized product of the Li-N2 battery. It can also be seen in the density of states that graphene with adsorption of 4N transforms from semiconducting to metallic properties. In addition, the differential charge also indicates that the Li-N2 material has a strong adsorption effect on the substrate, which can play the dual role of electricity storage and nitrogen fixation.

Mapping the correlations between bandgap, HOMO, and LUMO trends for meta substituted Zn-MOFs.

Bandgap is a key property that determines electrical and optical properties in materials. Modulating the bandgap thus is critical in developing novel materials particularly semiconductors with improved features. This study examines the bandgap, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) energy level trends in a metal organic framework, metal-organic framework 5 (MOF-5), as a function of Hammett substituent effect (with the constant σm in the meta-position of the benzene ring) and solvent dielectric effect (with the constant ε). Specifically, experimental design and response surface methodologies helped to assess the significance of trends and correlations between these molecular properties with σm and ε. While the HOMO and LUMO decrease with increasing σm, the LUMO exhibits greater sensitivity to the substituent's electron withdrawing capability. The relative difference in these trends helps to explain why the bandgap tends to decrease with increasing σm.

Excited Charge Separation in a π-Interacting Phenothiazine-Zinc Porphyrin-Fullerene Donor-Acceptor Conjugate.

We have designed, synthesized, and characterized a donor-acceptor triad, SPS-PPY-C60, that consists of a π-interacting phenothiazine-linked porphyrin as a donor and sensitizer and fullerene as an acceptor to seek charge separation upon photoexcitation. The optical absorption spectrum revealed red-shifted Soret and Q-bands of porphyrin due to charge transfer-type interactions involving the two ethynyl bridges carrying electron-rich and electron-poor substituents. The redox properties suggested that the phenothiazine-porphyrin part of the molecule is easier to oxidize and the fullerene part is easier to reduce. DFT calculations supported the redox properties wherein the electron density of the highest molecular orbital (HOMO) was distributed over the donor phenothiazine-porphyrin entity while the lowest unoccupied molecular orbital (LUMO) was distributed over the fullerene acceptor. TD-DFT studies suggested the involvement of both the S2 and S1 states in the charge transfer process. The steady-state emission spectrum, when excited either at porphyrin Soret or visible band absorption maxima, revealed quenched emission both in nonpolar and polar solvents, suggesting the occurrence of excited state events. Finally, femtosecond transient absorption spectral studies were performed to witness the charge separation by utilizing solvents of different polarities. The transient data was further analyzed by GloTarAn by fitting the data with appropriate models to describe photochemical events. From this, the average lifetime of the charge-separated state calculated was found to be 169 ps in benzonitrile, 319 ps in dichlorobenzene, 1.7 ns in toluene for Soret band excitation, and ∼320 ps for Q-band excitation in benzonitrile.

Tin Oxide/Amphiphilic Polymer Double‐Layered Hole Transporter for High‐Efficiency Tin Perovskite Solar Modules

AbstractAn exquisite, engineering of two poor hole transporting materials (HTMs, SnO, and PDTON) to form an excellent double‐layered HTL (SnO/PDTON) for inverted tin‐perovskite solar modules (TPSMs) is developed. SnO/PDTON has better photovoltaic performance than the commonly used PEDOT:PSS HTM when large‐area TPSMs are fabricated. Thermally evaporated SnO (that is a simple, available oxide with high hole mobility, good transparency, and adjustable frontier orbitals energy levels) film is used as a main hole transporting layer (HTL). Amphiphilic polymer PDTON (having the amine and ether groups on the side chains) film is used as a Co‐HTL, cross‐linker, passivator, and interface modification agent, as unveiled various physicochemical studies. Double‐layered SnO/PDTON with a flat morphology and good affinity toward perovskite precursor solution creates also a proper surface for depositing large‐area, high‐quality TPsk film. Therefore, TPSM (25.2 cm2 active area on 10 cm × 10 cm ITO substrate) based on double‐layered SnO/PDTON HTL achieving an efficiency over 10% with a negligible current hysteresis is reported for the first time. This study emphasizes not only the exquisite design of combining the specific characteristics of two prosaic HTMs to become a good double‐layered HTL but also gives a direction toward fabricating TPSMs to be applied in all‐perovskite tandem solar module.

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO–LUMO gaps

DFT calculations demonstrate that an isoacenofuran of any size possesses a smaller HOMO–LUMO gap than the corresponding acene bearing an isoelectronic π-system (i.e., the same total number of rings). Isoacenofurans show limited stability due in part to the highly reactive 1,3-carbons of the furan ring. Both 1,3-dimesitylisobenzofuran and 1,3-di(2’,4’,6’-triethylphenyl)isobenzofuran, each bearing sterically congesting ortho-alkyl groups on their phenyl substituents, have been synthesized and shown to adopt non-planar conformations with the ortho-alkyl groups located above and below the most reactive 1,3-carbons of the furan ring. These bulky substituents provide a strong measure of kinetic stabilization. Thus, 1,3-dimesitylisobenzofuran and 1,3-di(2’,4’,6’-triethylphenyl)isobenzofuran are significantly less reactive than 1,3-diphenylisobenzofuran toward the strong dienophiles DMAD and acrylonitrile. The insights gained here suggest that the synthesis of large, persistent, kinetically stabilized isoacenofurans with unusually small HOMO–LUMO gaps is achievable. As such, these molecules deserve increased attention as potential p-type organic semiconductors.

Cycloaddition reaction of methylidyne radical with dipyrromethanol: quantum chemical insights into the formation of di(pyridin-2-yl)methanol

Density functional theory was employed to investigate methylidyne radical reaction on to the unsaturation of dipyrromethanol moiety through cycloaddition forming a six membered di(pyridin-2-yl)methanol followed by H-elimination via ring expansion. Time-dependent density functional theory (TD-DFT) simulations were performed to figure out the ultraviolet–visible spectrum of dipyrromethanol and di(pyridin-2-yl)methanol. Ultraviolet–visible spectrum of dipyrromethanol and di(pyridin-2-yl)methanol shows that two sharp absorption peaks were obtained at λ max = 161 nm and 206 nm for the reactant dipyrromethanol while a sharp peak was observed for the product di(pyridin-2-yl)methanol at shorter wavelength (λ max = 170 nm). The theoretical IR spectrum of dipyrromethanol and di(pyridin-2-yl)methanol shows that a significant red shift of 129 cm−1 was observed in the case of di(pyridin-2-yl)methanol due to presence of two strong intra-molecular hydrogen bonds, which indicates its higher stability than the dipyrromethanol. HOMO–LUMO energy gap calculations and natural bond orbital (NBO) analysis endorse the type of electronic transition for the desired product di(pyridin-2-yl)methanol is π–π*. The global reactivity analysis shows the electron donor and acceptor nature of dipyrromethanol and methylidyne radical, respectively. A potential energy surface is constructed via methylidyne radical addition, ring expansion, and hydrogen elimination transition states. Thermodynamics study and potential energy surface of the title reaction indicates its highly exothermicity and spontaneous in nature.

On Entangled Singlet Pure Diradicals.

This work addresses a class of conjugated hydrocarbons that are expected to be singlet diradicals according to the topological Hückel Hamiltonian while possibly satisfying full on-bond electron pairing. These systems possess two degenerate singly occupied molecular orbitals (SOMOs), but aromaticity brought by properly positioned six-membered rings does prevent Jahn-Teller distortions. Density functional theory (DFT) calculations performed on two emblematic examples confirm the strong bond-length alternation in the closed-shell solutions and the clear spatial symmetry in the open-shell spin-unrestricted determinants, the latter solution always being found to have significantly lower energy. Since the SOMOs are here of different symmetry, the wave function is free from ionic valence-bond component, and spin decontamination of the unrestricted DFT solutions and wave function calculations at the CASSCF-plus-second-order-perturbation level confirm the expected pure diradical character of such molecules. In contrast to disjoint diradicals, the SOMOs of present systems have large amplitudes on neighbor atoms, and we propose to name them entangled pure diradicals, further providing some prescription rules for their design. Additional calculations point out the qualitative contrast between these molecules and the related diradicaloids.

Influence of benzothiophene acceptor moieties on the non-linear optical properties of pyreno-based chromophores: first-principles DFT framework.

Herein, a series of heterocyclic organic compounds (PYFD1-PYFD7) are designed with different acceptor moieties at the terminal position of a reference compound (PYFR) for nonlinear optical (NLO) active materials. The optoelectronic characteristics of the designed chromophores were investigated using density functional theory (DFT) calculations with the M06/6-311G(d,p) functional. Frontier molecular orbital (FMO) analysis revealed a significant decrease in the energy of the band gaps (2.340-2.602 eV) for the derivatives as compared to the PYFR reference compound (3.12 eV). An efficient transfer of charge from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) was seen, which was further corroborated by the density of states (DOS) and transition density matrix (TDM) heat maps. The results of the global reactivity parameters (GRPs) indicated that all derivatives exhibited greater softness (σ = 0.384-0.427 eV) and lower hardness (η = 0.394-1.302 eV) as compared to PYFR, indicating a higher level of polarizability in the derivatives. Moreover, all of the derivatives showed significant findings in terms of nonlinear optical (NLO) results as compared to the reference chromophore. PYFD2 showed the most effective NLO response (α = 1.861 × 10-22 and βtot = 2.376 × 10-28 esu), including a lowered band gap of 2.340 eV, the maximum softness value of 0.4273 eV, and the lowest hardness value of 1.170 eV as compared to other chromophores. The incorporation of different acceptors and thiophene as a π-spacer in this structural alteration significantly contributed to achieving remarkable NLO responses. Therefore, our findings may motivate experimentalists to synthesize these designed NLO active materials for the current advanced technological applications.

Synthesis and Experimental Structure of a Multifunctional Catechol‐Azomethinebenzoic Acid, DFT/DMol3 Calculations, and Molecular Docking with Hsp90

AbstractThe multifunctional catechol‐azomethine‐benzoic acid derivative 4‐[(E)‐[(2,3‐dihydroxyphenyl)methylidene]amino]benzoic acid (1) was prepared and the structure were confirmed by EI‐MS and 1H and 13C NMR spectroscopy. A Single‐crystal X‐ray diffraction study revealed coplanarity of the two aromatic rings within the imine function, supported by intramolecular N−H⋯O hydrogen bonds. In the crystal structure intermolecular O−H⋯O hydrogen bonds form chains, propagating along [010]. FT‐IR and Hirshfeld surface analysis confirms the multiple hydrogen bonding. DFT/DMol3 calculations localized the highest occupied molecular orbital (HOMO) on the o‐catechol unit, while the lowest unoccupied molecular orbital (LUMO) is delocalized over the entire molecule. The calculated map of electrostatic potential (MEP) showed relatively low values for both electrophilic and nucleophilic susceptibility. A molecular docking study of 1 in comparison with the established inhibitor geldanamycin (G) using the protein structure of the heat shock protein 90 co‐crystallized with G (Hsp90⋅G) showed that 1 occupies the same binding pocket as G in the Hsp90⋅G structure, indicating that the title structure might be a suitable inhibitor. The Swiss ADME approach showed promising general drug‐likeness properties for 1 with a relatively high lipophilicity (logP=1.68) and a logS value of −2.99 which lies in the middle of the logS distribution of traded drugs.

Intramolecular Charge Transfer and Stimuli-Responsive Emission in Cholesterol-Appended Phenothiazine-Cyanostyryl-Based Donor-Acceptor Systems.

Organic fluorescent molecules have received considerable attention owing to their various optoelectronic applications. Herein, we report the design and synthesis of two cholesterol-functionalized cyanostyrene-phenothiazine-based D-π-A systems that are emissive in both the solution and solid states. The newly synthesized cholesterol-appended phenothiazine-cyanostyrene diads PTCS-1 and PTCS-2 vary in the N-alkylation of phenothiazine, respectively, with─octyl and─hexyl chains. Both molecules are highly fluorescent and show reasonably good quantum yields in nonpolar solvents because of twisted intramolecular charge transfer (TICT). The molecules exhibit aggregation-induced emission in the solid state. Due to the presence of flexible alkyl chains in the phenothiazine and cholesterol moieties, PTCS-1 and PTCS-2 show mechanochromic luminescence switching in response to external shear stress and emission recovery under methanol vapor. Powder X-ray diffraction studies prove that the emission switching on the applied stimuli in both PTCS-1 and PTCS-2 is attributed to the reversible transformation between the crystalline and amorphous states. Time-dependent density functional theory (TD-DFT) studies are carried out to gain insight into the ICT interactions. TD-DFT analysis at the TD-M06-2X/def2-TZVP level further revealed that in both molecules, the lowest unoccupied molecular orbital (LUMO) + 2, LUMO, highest occupied molecular orbital (HOMO), and HOMO - 1 orbitals are responsible for the charge transfer interactions. These ICT interactions are identified as π-π* type interactions.

Understanding mechanism conversion in hydrogen evolution reaction on PtSe2: Role of layer number explored by density functional theory

The emerging two-dimensional (2D) transition metal dichalcogenide PtSe2 is a promising catalyst for hydrogen evolution reactions (HER). In this study, we performed density functional theory (DFT) calculations to investigate the mechanism conversion of the HER over PtSe2 with respect to the changes in the number of layers of the catalyst. We found that the adsorption energy of hydrogen (ΔGH) changed with an increase in the number of 2D material layers, and the most significant change occurred when the number of layers was increased from one to two. Furthermore, we conducted dynamic calculations to reveal the mechanisms of the HER on the basal and Vse surfaces. Owing to the changes in ΔGH, the HER mechanism undergoes a conversion between Volmer–Heyrovsky and Volmer–Volmer'–Tafel mechanisms. Through frontier orbitals analysis, layer-stacking altered the bonding capability between hydrogen and PtSe2 surfaces by altering the electronic structure of the PtSe2 surface. This study demonstrates the synergistic effect of interlayer interactions on the HER over PtSe2 catalysts and can be helpful in stimulating innovative ideas for 2D material design.

BeM(CO)3- (M = Co, Rh, Ir) and BeM(CO)3 (M = Ni, Pd, Pt): Triply bonded terminal beryllium in zero oxidation state.

We perform detailed potential energy surface explorations of BeM(CO)3- (M = Co, Rh, Ir) and BeM(CO)3 (M = Ni, Pd, Pt) using both single-reference and multireference-based methods. The present results at the CASPT2(12,12)/def2-QZVPD//M06-D3/def2-TZVPPD level reveal that the global minimum of BeM(CO)3- (M = Co, Rh, Ir) and BePt(CO)3 is a C3v symmetric structure with an 1A1 electronic state, where Be is located in a terminal position bonded to M along the center axis. For other cases, the C3v symmetric structure is a low-lying local minimum. Although the present complexes are isoelectronic with the recently reported BFe(CO)3- complex having a B-Fe quadruple bond, radial orbital-energy slope (ROS) analysis reveals that the highest occupied molecular orbital (HOMO) in the title complexes is slightly antibonding in nature, which bars a quadruple bonding assignment. Similar weak antibonding nature of HOMO in the previously reported BeM(CO)4 (M = Ru, Os) complexes is also noted in ROS analysis. The bonding analysis through energy decomposition analysis in combination with the natural orbital for chemical valence shows that the bonding between Be and M(CO)3q (q = -1 for M = Co, Rh, Ir and q = 0 for M = Ni, Pd, Pt) can be best described as Be in the ground state (1S) interacting with M(CO)30/- via dative bonds. The Be(spσ) → M(CO)3q σ-donation and the complementary Be(spσ) ← M(CO)3q σ-back donation make the overall σ bond, which is accompanied by two weak Be(pπ) ← M(CO)3q π-bonds. These complexes represent triply bonded terminal beryllium in an unusual zero oxidation state.

Synthesis, Characterization, and Properties of a Titanium(IV)-Tetrathiafulvalene-Based Complex.

To deeply investigate the interaction between a tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand 2a) was prepared. The stable complex formulated as Ti(1)2(2a), where 1 is a 2,2'-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti(1)2(2b)] were fully characterized in solution, and their solid-state structures were established by single-crystal X-ray diffraction analysis. Density functional theory calculations allowed the assignment of the frontier orbitals involved in the electronic transitions characterized by ultraviolet-visible absorption spectroscopy. Electrochemical and spectroelectrochemical studies revealed that the TTF unit within Ti(1)2(2a) can undergo two reversible one-electron oxidation processes; a reversible one-electron reduction of the Ti(IV) atom was highlighted. The photophysical measurements performed for this donor-acceptor molecular system indicated that an electron transfer process upon light excitation occurred within Ti(1)2(2a).

Enhancement of thermoelectric performance of thienoisoindigo based D‐A conjugated polymers through the incorporation of 3,4‐ethylenedioxythiophene as donor unit

AbstractWith the good planarity of conjugated backbone and high charge carrier mobilities, thienoisoindigo (TIIG)‐based polymers show great potential in organic electronic devices. In this work, two TIIG‐based D‐A conjugated polymers (PTIIG‐3T and PTIIG‐2T‐EDOT) were designed and synthesized, which exhibit high lying highest occupied molecular orbital (HOMO) energy level and can be facilely doped by FeCl3. Compared with PTIIG‐3T, one thiophene unit in the donor building block is replaced by 3,4‐ethylenedioxythiophene (EDOT) in PTIIG‐2T‐EDOT, and PTIIG‐2T‐EDOT shows a higher HOMO level with slightly higher coplanarity than PTIIG‐3T, which induce an enhancement in electrical conductivity after oxidation doping. After proper doping, doped PTIIG‐2T‐EDOT film achieved a higher TE power factor of 17.9 μW m−1 K−2 than that of PTIIG‐3T due to its higher conductivity. The results indicate that TIIG unit is a promising building block for future high‐performance conjugated polymers for thermoelectric applications, and incorporation of the EDOT unit into D‐A conjugated polymers could be an effective way to develop high performance thermoelectric polymers.

Solar-Driven Conversion of CO2 to C2 Products by the 3d Transition Metal Intercalates of Layered Lead Iodides.

Photocatalytic CO2 reduction to high-value-added C2+ products presents significant challenges, which is attributed to the slow kinetics of multi-e- CO2 photoreduction and the high thermodynamic barrier for C-C coupling. Incorporating redox-active Co2+/Ni2+ cations into lead halide photocatalysts has high potentials to improve carrier transport and introduce charge polarized bimetallic sites, addressing the kinetic and thermodynamic issues, respectively. In this study, a coordination-driven synthetic strategy is developed to introduce 3d transition metals into the interlamellar region of layered organolead iodides with atomic precision. The resultant bimetallic halide hybrids exhibit selective photoreduction of CO2 to C2H5OH using H2O vapor at the evolution rates of 24.9-31.4µmol g-1h-1 and high selectivity of 89.5-93.6%, while pristine layered lead iodide yields only C1 products. Band structure calculations and photoluminescence studies indicate that the interlayer Co2+/Ni2+ species greatly contribute to the frontier orbitals and enhance exciton dissociation into free carriers, facilitating carrier transport between adjacent lead iodide layers. In addition, Bader charge distribution calculations and in situ experimental spectroscopic studies reveal that the asymmetric Ni-O-Pb bimetallic catalytic sites exhibit intrinsic charge polarization, promoting C-C coupling and leading to the formation of the key *OC-CHO intermediate.

Studies of the nonlinear optical properties of a synthesized Schiff base ligand using visible cw laser beams

The synthesized Schiff base ligand (compound Z1) is analyzed by IR, mass, 1HNMR, and 13CNMR spectroscopies. Computational chemical modeling is performed to examine the geometry optimization and molecular structure of compound Z1 by using the DFT/ WB97XD/6-31+G(d,p) method. The parameters HOMO–LUMO energies with nonlinear optical (NLO) properties are computed. The results indicate good agreement between experimental and theoretical data, so that compound Z1 to have good NLO properties. The NLO properties of the compound Z1 are examined under excitation with a 473 nm, cw, low power laser beam via two techniques, viz., diffraction patterns (DPs) and the standard Z-scan techniques. As high as 3.03 × 10−11 m2 W−1 of the compound Z1 of the nonlinear refractive index (NLRI), n2, is obtained via the DPs. Both static and dynamic all –optical switching (SAOS and DAOS) are tested using 473 nm and 532 nm cw low power laser beams.

Dipole Moments Regulation of Biphosphonic Acid Molecules for Self-assembled Monolayers Boosts the Efficiency of Organic Solar Cells Exceeding 19.7.

PSS has been widely used as a hole extraction layer (HEL) in organic solar cells (OSCs). However, their acidic nature can potentially corrode the indium tin oxide (ITO) electrode over time, leading to adverse effects on the longevity of the OSCs. Herein, we have developed a class of biphosphonic acid molecules with tunable dipole moments for self-assembled monolayers (SAMs), namely, 3-BPIC(i), 3-BPIC, and 3-BPIC-F, which exhibit an increasing dipole moment in sequence. Compared to centrosymmetric 3-BPIC(i), the axisymmetric 3-BPIC and 3-BPIC-F exhibit higher adsorption energies (Eads) with ITO, shorter interface spacing, more uniform coverage on ITO surface, and better interfacial compatibility with the active layer. Thanks to the incorporation of fluorine atoms, 3-BPIC-F exhibits a deeper highest occupied molecular orbital (HOMO) energy level and a larger dipole moment compared to 3-BPIC, resulting in an enlarged work function (WF) for the ITO/3-BPIC-F substrate. These advantages of 3-BPIC-F could not only improve hole extraction within the device but also lower the interfacial impedance and reduce nonradiative recombination at the interface. As a result, the OSCs using SAM based on 3-BPIC-F obtained a record high efficiency of 19.71%, which is higher than that achieved from the cells based on 3-BPIC(i) (13.54%) and 3-BPIC (19.34%). Importantly, 3-BPIC-F-based OSCs exhibit significantly enhanced stability compared to that utilizing PEDOT:PSS as HEL. Our work offers guidance for the future design of functional molecules for SAMs to realize even higher performance in organic solar cells.

Mobility inhibition of arsenic in the soil: the role of green synthesized silica nanoparticles

The studies showed the effectiveness of green-synthesized SiO2NPs in mitigating the toxicity of Arsenic. Density Functional Theory (DFT) is a computational method used to determine electronic structure, energy gap, and toxicity prediction. Experimentally, silicon nanoparticles of 0 (S0) and 100% v/v (S100) were applied to the surface of the soil. 150 mL of Arsenic trioxide was applied twice at a rate of 0 (As0) and 3.2 g/mL (As3.2) at an interval of three weeks. Green synthesized SiO2NPs possessed a higher chemical potential (µ) and electrophilicity index; consequently, charges could be transferred and easily polarized. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of the green synthesized SiO2NPs enable them to donate electrons and complex with arsenic, reducing their bioavailability and toxicity. Evidence from the studies further showed that SiO2NPs had buffered the soil acidity and electric conductivity, posing a high binding site and reactivity with exchangeable cations and micronutrients due to their smaller energy gap. Furthermore, the catalytic activities of the soil enzymes dehydrogenase (DHA) and peroxidase (POD) were greatly increased, which enhanced the electrostatic interaction between the SiO2NPs and As.

Tunable Unexplored Luminescence in Waveguides Based on D-A-D Benzoselenadiazoles Nanofibers

A set of novel Donor-Acceptor-Donor (D-A-D) benzoselenadiazole derivatives has been synthesized and crystallized in nanocrystals in order to explore the correlation between their chemical structure and the waveguided luminescent properties. The findings reveal that all crystals exhibit luminescence and active optical waveguiding, demonstrating the ability to adjust their luminescence within a broad spectral range of 550–700 nm depending on the donor group attached to the benzoselenadiazole core. Notably, a clear relationship exists between the HOMO-LUMO energy gaps of each compound and the color emission of the corresponding optical waveguides. These outcomes affirm the feasibility of modifying the color emission of organic waveguides through suitable chemical functionalization. Importantly, this study marks the first utilization of benzoseleniadiazole derivatives for such purposes, underscoring the originality of this research. In addition, the obtention of nanocrystals is a key tool for the implementation of miniaturized photonic devices.