Strontium isotopes track female dispersal in Taï chimpanzees.

OBJECTIVES: Chimpanzees (Pan troglodytes) are patrilocal, with males remaining in their natal community and females dispersing when they reach sexual maturity. However, the details of female chimpanzee dispersal, such as their possible origin, are difficult to assess, even in habituated communities. This study investigates the utility of 87Sr/86Sr analysis for (1) assessing Sr baseline differences between chimpanzee territories and (2) identifying the status (immigrant or natal) of females of unknown origin within the territories of five neighboring communities in Taï National Park (Côte d'Ivoire). MATERIALS AND METHODS: To create a local Sr isoscape for the Taï Chimpanzee Project (TCP) study area, we sampled environmental samples from TCP-established territories (n = 35). To assess dispersal patterns, 34 tooth enamel samples (one per individual) were selected from the Taï chimpanzee skeletal collection. 87Sr/86Sr analysis was performed on all 69 samples at the W.M. Keck Lab. The theoretical density and overlap of chimpanzee communities as well as generalized linear mixed models (GLMMs) were used to test each question. RESULTS: 87Sr/86Sr ratios for natal male chimpanzees ranged from 0.71662 to 0.72187, which is well within the corresponding environmental baseline range of 0.70774-0.73460. The local Sr isoscapes fit was estimated with the root-mean-square error value, which was 0.0048 (22% of the whole 87Sr/86Sr data range). GLMMs identified significant differences in 87Sr/86Sr ratios between natal and unknown North community origin groups, suggesting that after 1980, females of unknown origin could be immigrants to North community (n = 7, z-ratio = -4.08, p = 0.0001, power = 0.94). DISCUSSION: This study indicates that 87Sr/86This study indicates that 87Sr/86Sr analysis can successfully identify immigrant females in skeletal collections obtained from wild chimpanzee communities, enabling the tracking of female dispersal patterns historically. There are, however, significant limitations within the scope of this study, such as (1) the absence of reliable maps for the TCP study area, (2) limited capacity for environmental sampling, (3) small sample sizes, and (4) tooth formation in wild chimpanzees.

Ferrocene-based metal-organic frameworks with dual synergistic active sites for selectively electrochemical removal of arsenic from contaminated water.

The effective removal of trace levels of the highly toxic arsenite (As(Ⅲ)) from groundwater is crucial to address the threat to drinking water supply. Herein, we developed an electrochemical separation system utilizing redox-active ferrocene-based metal-organic frameworks (termed Fe-DFc) for selective removal of As(III). This system leveraged 1,1'-ferrocenedicarboxylic acid as a ligand coordinated with iron, enabling the highly selective capture and conversion of As(III) from groundwater. The Fe-DFc electrode-based electrochemical system not only effectively removed As(III) even in the presence of a 1250-fold excess of competing electrolytes, but also converted about 96 % of the adsorbed As(III) into the less toxic As(V), surpassing the results of those documented in the current literature. X-ray absorption fine structure analysis and density functional theory calculations demonstrated that the high selectivity of Fe-O6 moiety and the exceptional redox activity of Fc synergistically contributed to the efficient removal of As(III). Moreover, the electrochemical separation system enabled the remediation of arsenic-contaminated groundwater at a low energy cost of 0.033 kWh m-3 during long-term operation, highlighting the application potential of the electrochemical technology for arsenic removal from contaminated water.

A sequencing electroreduction-electrooxidation system driven by atomic hydrogen for enhancing 2,4-dichloronitrobenzene removal from wastewater.

The sequencing electroreduction-electrooxidation process has emerged as a promising approach for the degradation of the chloronitrobenzenes (CNBs) due to its elimination of electro-withdrawing groups in the reduction process, facilitating further removal in the subsequent oxidation process. Herein, we developed a cathode consisting of atom Pd on a Ti plate, which enabled the electro-generation of atomic hydrogen (H*) and the efficient electrocatalytic activation of H2O2 to hydroxyl radical (•OH). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra verified the existence of H* and •OH. The electroreduction-electrooxidation system achieved 94.7% of 20 mg L-1 2,4-DCNB removal with a relatively low H2O2 addition (5 mM). Moreover, the inhibition rate of Photobacterium phosphoreum in the effluent decreased from 95% to 52% after the sequencing electroreduction-electrooxidation processes. It was further revealed that the H* dominated the electroreduction process and triggered the electrooxidation process. Our work sheds light on the effective removal of electron-withdrawing groups substituted aromatic contaminants from water and wastewater.

Electrochemical oxidation of reverse osmosis concentrate using a pilot-scale reactive electrochemical membrane filtration system: Performance and mechanisms.

Scale-up treatment of real wastewater holds the key to promoting the practical application of electrochemical filtration technology. This work used a pilot-scale Ti/Pd reactive electrochemical membrane (REM) system (12 REM modules with a total REM area of 0.144 m2) to treat high-salinity reverse osmosis concentrate (ROC) from a chemical industry park. The pilot-scale Ti/Pd REM system demonstrated effective electrochemical degradation of ROC wastewater, achieving removal efficiencies of 82.3 ± 1.9% for COD and 46.7 ± 5.6% for TN at a membrane flux of 90 L/(m2·h) and a cell voltage of 5 V, with an energy consumption of 0.045 kWh/g-COD. Singlet oxygen (1O2) and reactive chlorine species were identified as the two primary reactive oxygen species generated in the Ti/Pd REM system. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis indicated that the pilot-scale Ti/Pd REM treatment effectively oxidized humic acid-like substance and unsaturated aromatic compounds. Overall, the Ti/Pd REM technology shows a promising application potential for the treatment of high-salinity ROC from the chemical industry.

Anaerobic hydrolysis of recalcitrant tetramethylammonium from semiconductor wastewater: Performance and mechanisms.

The treatment of tetramethylammonium hydroxide (TMAH)-bearing wastewater, generated in the electronic and semiconductor industries, raises significant concerns due to the neurotoxic, recalcitrant, and bio-inhibiting effects of TMAH. In this study, we proposed the use of an anaerobic hydrolysis bioreactor (AHBR) for TMAH removal, achieving a high removal efficiency of approximately 85%, which greatly surpassed the performance of widely-used advanced oxidation processes (AOPs). Density functional theory calculations indicated that the unexpectedly poor efficiency (5.8-8.0%) of selected AOPs can be attributed to the electrostatic repulsion between oxidants and the tightly bound electrons of TMAH. Metagenomic analyses of the AHBR revealed that Proteobacteria and Euryarchaeota played a dominant role in the transformation of TMAH through processes such as methyl transfer, methanogenesis, and acetyl-coenzyme A synthesis, utilizing methyl-tetrahydromethanopterin as a substrate. Moreover, several potential functional genes (e.g., mprF, basS, bcrB, sugE) related to TMAH resistance have been identified. Molecular docking studies between five selected proteins and tetramethylammonium further provided evidence supporting the roles of these potential functional genes. This study demonstrates the superiority of AHBR as a pretreatment technology compared to several widely-researched AOPs, paving the way for the proper design of treatment processes to abate TMAH in semiconductor wastewater.

Preparation of a Molecularly Imprinted Silica Nanoparticles Embedded Microfiltration Membrane for Selective Separation of Tetrabromobisphenol A from Water.

The ubiquitous presence of tetrabromobisphenol A (TBBPA) in aquatic environments has caused severe environmental and public health concerns; it is therefore of great significance to develop effective techniques to remove this compound from contaminated waters. Herein, a TBBPA imprinted membrane was successfully fabricated via incorporating imprinted silica nanoparticles (SiO2 NPs). The TBBPA imprinted layer was synthesized on the 3-(methacryloyloxy) propyltrimethoxysilane (KH-570) modified SiO2 NPs via surface imprinting. Eluted TBBPA molecularly imprinted nanoparticles (E-TBBPA-MINs) were incorporated onto a polyvinylidene difluoride (PVDF) microfiltration membrane via vacuum-assisted filtration. The obtained E-TBBPA-MINs embedded membrane (E-TBBPA-MIM) showed appreciable permeation selectivity toward the structurally analogous to TBBPA (i.e., 6.74, 5.24 and 6.31 of the permselectivity factors for p-tert-butylphenol (BP), bisphenol A (BPA) and 4,4'-dihydroxybiphenyl (DDBP), respectively), far superior to the non-imprinted membrane (i.e., 1.47, 1.17 and 1.56 for BP, BPA and DDBP, respectively). The permselectivity mechanism of E-TBBPA-MIM could be attributed to the specific chemical adsorption and spatial complementation of TBBPA molecules by the imprinted cavities. The resulting E-TBBPA-MIM exhibited good stability after five adsorption/desorption cycles. The findings of this study validated the feasibility of developing nanoparticles embedded molecularly imprinted membrane for efficient separation and removal of TBBPA from water.

Removal of p-toluenesulfonic acid from wastewater using a filtration-enhanced electro-Fenton reactor.

Rapid global industrialization accompanies the discharge of industrial wastewater. p-Toluenesulfonic acid (PTSA), a kind of aromatic sulfonate that belongs to the refractory organic pollutant, is one of the most widely used chemicals in pharmaceutical, dye, petrochemical and plastic industries. In this study, we developed a filtration-enhanced electro-Fenton (FEEF) reactor to remove PTSA from synthetic wastewater. A filtration-enhanced stainless-steel mesh (FESSM) was used as the cathode. Under the optimal operating conditions of applied voltage 2.5 V, pH = 3.0, addition of 0.2 mM Fe2+ and 1.0 mM H2O2 for 120 min, the removal efficiency of PTSA (initial concentration of 100 mg L-1) could reach 92.6%. Compared with the control anodic oxidation and conventional Fenton system, the FEEF system showed higher ˙OH yield and PTSA removal efficiency, with a lower effluent biological toxicity and operating cost. The enhanced mass transfer rate by the filtration in the FEEF system accelerated the regeneration of catalyst Fe2+ and further promoted the heterogeneous reactions. The Fe species on the surface of FESSM cathode possessed a gradient distribution, the inner layer was dominated by Fe and the outer layer was Fe3+. The degradation pathways of PTSA were proposed, including methyl hydroxylation, sulfonyl hydroxylation, ß-hydrogen hydroxylation, and ring-opening reaction. These results demonstrate that the novel FEEF system is a promising technology for the removal of refractory organic pollutants from industrial wastewater.

Membrane fouling behaviors in a full-scale zero liquid discharge system for cold-rolling wastewater brine treatment: A comprehensive analysis on multiple membrane processes.

The challenge of water scarcity drives zero liquid discharge (ZLD) treatment to maximize reuse of industrial wastewater. Deciphering the characteristics and mechanisms of membrane fouling in the membrane-based ZLD system is crucial for the development of effective fouling control strategies. However, current studies only focused on the membrane fouling of single step, lacking in-depth understanding on the ZLD systems using multiple membrane processes. Herein, membrane fouling characteristics and mechanisms in a full-scale ZLD system for cold-rolling wastewater brine treatment were investigated via a comprehensive analysis on multiple nanofiltration (NF) and reverse osmosis (RO) membrane processes. The membrane fouling behaviors showed distinct characteristics along the wastewater flow direction in the ZLD system. Increasing amounts of foulants were deposited on the membrane surfaces with the sequence of the 1st pass RO, 1st stage NF, and 2nd stage NF processes. The organic fouling and silica scaling were more intensive in the 1st stage NF and 2nd stage NF for treating the brine of the 1st pass RO, as the foulants were rejected and concentrated by previous membrane processes. Severe inorganic fouling, containing amorphous SiO2, Al2O3, and Al2SiO5, occurred on the membrane surface of the 2nd pass RO membrane, due to the recirculated high-concentration silica, high water recovery, and concentration polarization. For the 3rd pass RO process, both the amounts of organic and inorganic foulants decreased dramatically, due to the low foulant concentration in its influent. This work provides a comprehensive understanding of membrane fouling in a membrane-based ZLD system, facilitating the development of membrane fouling control strategies for multiple membrane processes.

Study on the heterogeneity of China's agricultural economic growth in the context of temperature shocks.

Under the background of the new development concept, compared with the absolute impacts, the relative impacts of climate change on agricultural growth deserve more attention. Based on the data from China for years 1991 and 2018, this paper uses historical fluctuations in temperature within cities to identify the heterogeneous effects on aggregate agricultural outcomes during farming and fallow periods. The results show that: first, as temperature rises reduce the economic growth rate of each agricultural sector, and the areas that are relatively vulnerable (i.e., areas where disposable income of farm households is below the sample mean) are more significantly affected by the negative impact of temperature rise; second, the impact of temperature rise on agricultural economic growth is mainly concentrated in the farming period, while the marginal damage of temperature rise is on a decreasing trend; third, the heterogeneous impact of temperature rise on agricultural economic growth during the agricultural fallow period is also not negligible. At the same time, its impact on agricultural economy is still in the primary stage, that is, its marginal damage tends to increase with the increase in temperature fluctuation. These results inform identifying the climate's role in agricultural development and provide a theoretical and operational perspective for further optimizing the adaptive policy systems. With wide coverage of adaptive technology, we should pay more attention to the even distribution of technological dividends and continuously improve the coping ability of vulnerable groups.

Mechanistic insights into CO2 pressure regulating microbial competition in a hydrogen-based membrane biofilm reactor for denitrification.

CO2 is a proven pH regulator in hydrogen-based membrane biofilm reactor (H2-MBfR) but how its pressure regulates microbial competition in this system remains unclear. This work evaluates the CO2 pressure dependent system performance, CO2 allocation, microbial structure and activity of CO2 source H2-MBfR. The optimum system performance was reached at the CO2 pressure of 0.008 MPa, and this pressure enabled 0.18 g C/(m2·d) of dissolved inorganic carbon (DIC) allocated to denitrifying bacteria (DNB) for carbon source anabolism and denitrification-related proton compensation, while inducing a bulk liquid pH (pH 7.4) in favor of DNB activity by remaining 0.21 g C/(m2·d) of DIC as pH buffer. Increasing CO2 pressure from 0.008 to 0.016 MPa caused the markedly changed DNB composition, and the diminished DNB population was accompanied by the enrichment of sulfate-reducing bacteria (SRB). A high CO2 pressure of 0.016 MPa was estimated to induce the enhanced SRB activity and weakened DNB activity.

Biofouling suppresses effluent toxicity in an electrochemical filtration system for remediation of sulfanilic acid-contaminated water.

Electrochemical filtration system (EFS) has received broad interest due to its high efficiency for organic contaminants removal. However, the porous nature of electrodes and flow-through operation mode make it susceptible to potential fouling. In this work, we systematically investigated the impacts of biofouling on sulfanilic acid (SA) removal and effluent toxicity in an EFS. Results showed that the degradation efficiency of SA slightly deteriorated from 92.3% to 81.1% at 4.0 V due to the electrode fouling. Surprisingly, after the occurrence of fouling, the toxicity (in terms of luminescent bacteria inhibition) of the EFS effluent decreased from 72.3% to 40.2%, and cytotoxicity assay exhibited similar tendency. Scanning electron microscopy and confocal laser scanning microscopy analyses revealed that biofouling occurred on the porous cathode, and live microorganisms were the dominant contributors, which are expected to play an important role in toxicity suppression. The relative abundance of Flavobacterium genus, related to the degradation of p-nitrophenol (an aromatic intermediate product of SA), increased on the membrane cathode after fouling. The analysis of degradation pathway confirmed the synergetic effects of electrochemical oxidation and biodegradation in removal of SA and its intermediate products in a bio-fouled EFS, accounting for the decrease of the effluent toxicity. Results of our study, for the first time, highlight the critical role of biofouling in detoxication using EFS for the treatment of contaminated water.

Theoretical study on pentiptycene molecular brake: photoinduced isomerization and photoinduced electron transfer.

The isomerization of the double bond plays an important role in the braking and de-braking of the light-controlled molecular brake. Therefore, the pentiptycene-type (Pp-type) light-controlled molecular brake system ((E)- and (Z)-4'-pentiptycyl vinyl-[1,1'-biphenyl]-4-carbonitrile) containing the C = C double bond was theoretically studied. Combining the 6-31G(d) basis set, the ωB97XD functional with dispersion correction was applied to implement the (E)-configuration and (Z)-configuration initial optimization. Next, using the 6-311G(d,p) basis set, the relaxed potential energy surface scans of the rotation angle were operated, and then the optimization calculations of the transition states at the extremum high points. Analyzing the stagnation points and the rotational transition states on the potential energy profiles, the rotation mechanism and basic energy parameters of the molecular brake were obtained. Then, the DFT computations at ground states and the TD-DFT computations of vertical excitation energy were put into practice at the accuracy of the def-TZVP basis set for the two configurations, and using the natural transition orbital (NTO) analyses combining the excitation energies and absorption spectra, the electronic transition characteristics and electron transfer properties of light-controlled molecular brake were studied. Afterwards, in order to investigate the photoinduced isomerization reaction, the C = C double bond was scanned on the relaxed potential energy surface, and the intermediates of the isomerization reaction were searched and analyzed; thus, the braking mechanism of the light-controlled molecular brake was proposed.

Organic Persistent Luminescent Materials: Ultralong Room-Temperature Phosphorescence and Multicolor-Tunable Afterglow.

Organic persistent luminescent materials have attracted special attention due to their significant applications in optoelectronics, sensors, and security technology areas. In this work, a series of organic compounds (1-4) with twisted electron donor-acceptor structures are successfully designed and synthesized, and then the resultant compounds are dissolved in methyl methacrylate (MMA), and afterward, in situ polymerization realizes single-molecular organic room-temperature phosphorescent (RTP) materials (P1-P4). All RTP materials show long lifetime, especially P2 exhibits ultralong lifetime of 1.51 s. When the compounds are grown into single crystals, multicolor-tunable afterglow is obtained at different delay times due to the dual emission of phosphorescence and delayed fluorescence, which is promising to be applied in high-level anticounterfeiting.

An electrochemical membrane biofilm reactor for removing sulfonamides from wastewater and suppressing antibiotic resistance development: Performance and mechanisms.

Sulfonamides, such as sulfadiazine (SDZ), are frequently detected in water and wastewater with their toxic and persistent nature arousing much concern. In this work, a novel electrochemical membrane biofilm reactor (EMBfR) was constructed for the removal of SDZ whilst suppressing the development of antibiotic resistance genes (ARGs). Results showed that the EMBfR achieved 94.9% removal of SDZ, significantly higher than that of a control membrane biofilm reactor (MBfR) without electric field applied (44.3%) or an electrolytic reactor without biofilm (77.3%). Moreover, the relative abundance of ARGs in the EMBfR was only 32.0% of that in MBfR, suggesting that the production of ARGs was significantly suppressed in the EMBfR. The underlying mechanisms relate to (i) the change of the microbial community structure in the presence of the electric field, leading to the enrichment of potential aromatic-degrading microorganisms (e.g., Rhodococcus accounting for 51.0% of the total in the EMBfR compared to 10.0% in the MBfR) and (ii) the unique degradation pathway of SDZ in the EMBfR attributed to the synergistic effect between the electrochemical and biological processes. Our study highlights the benefits of EMBfR in removing pharmaceuticals from contaminated waters and suppressing the development (and transfer) of ARGs in the environment.

Self-Enhanced Decomplexation of Cu-Organic Complexes and Cu Recovery from Wastewaters Using an Electrochemical Membrane Filtration System.

Heavy metals in industrial wastewaters are typically present as stable metal-organic complexes with their cost-effective treatment remaining a significant challenge. Herein, a self-enhanced decomplexation scenario is developed using an electrochemical membrane filtration (EMF) system for efficient decomplexation and Cu recovery. Using Cu-EDTA as a model pollutant, the EMF system achieved 81.5% decomplexation of the Cu-EDTA complex and 72.4% recovery of Cu at a cell voltage of 3 V. The •OH produced at the anode first attacked Cu-EDTA to produce intermediate Cu-organic complexes that reacted catalytically with the H2O2 generated from the reduction of dissolved oxygen at the cathode to initiate chainlike self-enhanced decomplexation in the EMF system. The decomplexed Cu products were further reduced or precipitated at the cathodic membrane surface thereby achieving efficient Cu recovery. By scavenging H2O2 (excluding self-enhanced decomplexation), the rate of decomplexation decreased from 8.8 × 10-1 to 4.1 × 10-1 h-1, confirming the important role of self-enhanced decomplexation in this system. The energy efficiency of this system is 93.5 g kWh-1 for Cu-EDTA decomplexation and 15.0 g kWh-1 for Cu recovery, which is much higher than that reported in the previous literature (i.e., 7.5 g kWh-1 for decomplexation and 1.2 g kWh-1 for recovery). Our results highlight the potential of using EMF for the cost-effective treatment of industrial wastewaters containing heavy metals.

Theoretical study of switching characteristics of molecular tweezers based on bis(Zn-salphen).

A series of novel tweezers based on bis(Zn-salphen) complex is theoretically studied. Density functional theory (DFT) method is used to investigate the switchable properties of terpy/bis(Zn-salphen) complex (1, terpy=2,2':6',2″-terpyridine) and Br-phtpy/bis(Zn-salphen) complex (2, Br-phtpy=4'-bromophenyl-2,2':6',2″-terpyridine). In this study, the free tweezers 1 and 2 can be converted from a "W" open form to a "U" closed form upon Ru(III) coordination. The switching performances were characterized by 1H NMR and absorption spectra. DFT calculations were carried out using a B3LYP-D3 functional and def2-SVP basis set for all atoms. 1H NMR spectra showed that terpyridine protons had an obvious upfield shift during complexation with RuCl3. The absorption spectrum was observed in the closed tweezers with a significant red shift and a decreased oscillator strength. In addition, the tweezers were reopened by introducing molecule pyrazine in the "U"-shaped conformation to form a host-guest system. The recognition ability of two Zn-salphen complexes was studied by geometrical optimization and absorption spectra.

Dually Charged MOF-Based Thin-Film Nanocomposite Nanofiltration Membrane for Enhanced Removal of Charged Pharmaceutically Active Compounds.

Removal of pharmaceutically active compounds (PhACs) is of great importance in wastewater reclamation due to their potent negative impacts on human health. Typical polyamide nanofiltration (NF) membranes are negatively charged, which compromises their rejection rate of positively charged PhACs. Herein, we propose to rationally design a novel thin-film nanocomposite (TFN) NF membrane featuring a dually charged metal organic framework (MOF) to effectively remove both positively and negatively charged PhACs. Ethylenediamine (ED) was grafted to the coordinately unsaturated metal sites inside the MIL-101(Cr). The resulting ED-MIL-101(Cr) contained both strong positively charged amine groups inside its channels and negatively charged carboxyl groups at its surface. This dually charged nature of the MOF nanoparticles enabled the ED-MIL-101(Cr)-containing TFN membrane to achieve high rejection rates (mostly >90%) for both positively (terbutaline, atenolol, fluoxetine) and negatively charged PhACs (ketoprofen, diclofenac, bezafibrate). At the same time, the ED-MIL-101(Cr) TFN membrane had greatly improved water permeance (140% over the control membrane with MOF loading). Calculations based on density functional theory further confirmed the large energy barrier for the migration of both negatively and positively charged PhACs across the nanochannels of ED-MIL-101(Cr). This study highlights a promising potential of dually charged MOF-TFN membranes for efficient removal of trace organic contaminants in wastewater reclamation.

Enhanced isophthalonitrile complexation-reduction removal using a novel anaerobic fluidized bed reactor in a bioelectrochemical system based on electric field activation (AFBR-EFA).

On account of the recalcitrant and highly toxicity of organonitrile substrates, traditional processes are limited by HCN poisoning thus inefficient. This article proposed a novel anaerobic fluidized bed reactor with electric field activation (AFBR-EFA) which had a 260-day continuous operation. The operation aims to explore the practicability of the enhanced reduction of isophthalonitrile (IPN), with emphasis on the optimum operation parameters and synergistic effect between electric field and anaerobic processes. The results showed that relatively higher voltage (1.0 V < V < 1.6 V) had a positive impact on reduction enhancement. High removal could be obtained at high initial concentration, low methanol dosage and short HRT which indicated that tolerance to shock loading was significantly enhanced in AFBR-EFA. Furthermore, EFA visibly motivated the enrichment of electrochemically active bacteria and various autotrophic IPN degradation-related species. The significantly efficient performance makes the potential for full-scale application of the AFBR-EFA markedly improved, particularly for treating hard-biodegraded contaminants.

Theoretical study on noncovalent interaction of molecular tweezers by Zn(II) salphen-azo-crown ether triads receptor.

A novel zinc(II)-salphen-azo-benzo-15-crown-5 triad receptor was studied theoretically as ditopic recognition of hydrophobic amino acid. And density functional theory was used to investigate the Zn(II) salphen-crown ether complex (L1), complex L2 (L1 with the alkaline metal cation Na+), and the corresponding 1:1 sandwich complex (complex L with tryptophan). In this work, geometrical optimization was carried out using ωB97XD functional and def2-SVP basis set for all atoms. The absorption spectra and excited-states were calculated using time-dependent density functional theory and ωB97XD/def2-TZVP level. The absorption spectra data show some significantly shifts in the absorption band due to the present of Na+ or tryptophan. In addition, interfragment interactions between receptor L and tryptophan were analyzed in detail by Independent Gradient Model and topological properties of Bader's atoms in molecules theory, which is found to contribute to forming the metal-ligand bonds, intermolecular H-bond, and van der Waals interaction in 1:1 sandwich complex. The above results demonstrate that the L2 complex is a ditopic receptor to be utilized to recognize amphiphilic molecule - tryptophan.

Theoretical study of D-A'-π-A/D-π-A'-π-A triphenylamine and quinoline derivatives as sensitizers for dye-sensitized solar cells.

We have designed four dyes based on D-A'-π-A/D-π-A'-π-A triphenylamine and quinoline derivatives for dye-sensitized solar cells (DSSCs) and studied their optoelectronic properties as well as the effects of the introduction of alkoxy groups and thiophene group on these properties. The geometries, single point energy, charge population, electrostatic potential (ESP) distribution, dipole moments, frontier molecular orbitals (FMOs) and HOMO-LUMO energy gaps of the dyes were discussed to study the electronic properties of dyes based on density functional theory (DFT). And the absorption spectra, light harvesting efficiency (LHE), hole-electron distribution, charge transfer amount from HOMO to LUMO (Q CT), D index, H CT index, S m index and exciton binding energy (E coul) were discussed to investigate the optical and charge-transfer properties of dyes by time-dependent density functional theory (TD-DFT). The calculated results show that all the dyes follow the energy level matching principle and have broadened absorption bands at visible region. Besides, the introduction of alkoxy groups into triarylamine donors and thiophene groups into conjugated bridges can obviously improve the stability and optoelectronic properties of dyes. It is shown that the dye D4, which has had alkoxy groups as well as thiophene groups introduced and possesses a D-π-A'-π-A configuration, has the optimal optoelectronic properties and can be used as an ideal dye sensitizer.