Computational insights into the underlying mechanism of zinc ion-specificity of the fluorescent probe, BDA-1.

Ion specificity is crucial for developing fluorescence probes. Using a recently reported optical sensor (BDA-1) of Zn2+ as a representative, we carried out extensive quantum chemical calculations on its photophysical properties using density function theory. According to the calculated optimized geometries, excitation energies and transition oscillator strengths, the weak fluorescence of BDA-1 observed in experiments is attributed to the suppression of fluorescence emission by efficient internal conversion, rather than the previously proposed photoinduced electron transfer (PET) mechanism. With the addition of Zn2+ or Cd2+ ions, the tetradentate chelates [M:BDA-1-H+]+ (M=Zn, Cd) are produced. According to frontier molecular orbital and interfragment charge transfer analyses of these complexes, PET is preferentially confirmed to occur upon photo-excitation. Notably, as one coordination bond in the excited [Cd:BDA-1-H+]+ complex is significantly weakened in comparison to that of [Zn:BDA-1-H+]+, their molecular orbital compositions in the S1 state are completely different. As a result, absorption and radiation transitions of [Zn:BDA-1-H+]+ both have considerable oscillator strength, while fluorescence radiation from the excited [Cd:BDA-1-H+]+ is doubly suppressed. This difference causes that the fluorescence intensity of BDA-1 is sensitive to the addition of metal ions, and exhibits the zinc ion-specificity.

Structural Study of [Sc3O4(CO2)n]+ (n = 2, 3) Complexes by Infrared Photodissociation Spectroscopy and Density Functional Calculations.

The catalytic transformation of CO2 into valuable products has garnered wide interest owing to both economic and environmental benefits, in which the chemical fixation of CO2 into carbonate structures represents a crucial step that occurs on the adsorbed catalyst surfaces. Transition metal oxides with acidic and basic active sites have exhibited potential in promoting the carbonation of weakly bound CO2 molecules. Here, the interactions between CO2 molecules and the Sc3O4+ cation in the gas phase are investigated by using infrared photodissociation spectroscopy in conjunction with quantum chemical calculations. Both end-on and various carbonate-containing configurations, including center and bridge carbonate structures, have been theoretically identified for the CO2-coordinated ion-molecule complexes. Based on the comparison between the experimental spectra and simulated spectra of low-lying isomers in the CO2 antisymmetric stretching vibrational frequency region, isomers characterized by a bridge carbonate core structure are demonstrated to be the major contributors to the observed spectra. Examination of potential energy surfaces reveals lower energy barriers and simpler reaction routes for the conversion of molecularly bound CO2 into a bridge carbonate moiety, providing reasonable explanations for their prevalence in the experiments.

The N+ Formation Mechanism of Vibrationally Selected N2O+ Ions in the C2Σ+ State: A TPEPICO Imaging Study.

The N-NO bond fission of N2O+(C2Σ+) ions can produce two major fragment ions, NO+ or N+. In contrast to the dominant NO+ fragment ion, the N+ formation mechanism remains unclear to date. Here, dissociative photoionization of N2O via the C2Σ+ ionic state has been reinvestigated using a combined approach of threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging and quantum chemical calculations. Accompanying the N+(3P) formation, the NO(X2Π) neutral fragment with low and high vi-rotational distributions was identified, based on the N+ speed and angular distributions derived from the TPEPICO images. In particular, the excitation of the symmetric stretching ν1+ mode promotes the formation of high rotational components, while the asymmetric stretching ν3+ mode shows the exact opposite effect. According to our calculated multistate potential energy surfaces, intersystem crossing from C2Σ+ to 14Π exclusively provides feasible decomposition pathways to produce the N+ fragment. In a slightly bent geometry, spin-orbit couplings between C2Σ+ and two substates of 14Π, 14A' or 14A″, play a crucial role in the N+ formation from vibrationally selected N2O+(C2Σ+) ions. The mechanism also provides new insights into the charge transfer reaction of N+ + NO → N + NO+.

Water-Ice Microstructures and Hydration States of Acridinium Iodide Studied by Phosphorescence Spectroscopy.

Ice has been suggested to have played a significant role in the origin of life partly owing to its ability to concentrate organic molecules and promote reaction efficiency. However, the techniques for studying organic molecules in ice are absorption-based, which limits the sensitivity of measurements. Here we introduce an emission-based method to study organic molecules in water ice: the phosphorescence displays high sensitivity depending on the hydration state of an organic salt probe, acridinium iodide (ADI). The designed ADI aqueous system exhibits phosphorescence that can be severely perturbed when the temperature is higher than 110 K at a concentration of the order of 10-5 M, indicating changes in hydration for ADI. Using the ADI phosphorescent probe, it is found that the microstructures of water ice, i.e., crystalline vs. glassy, can be strongly dictated by a trace amount (as low as 10-5 M) of water-soluble organic molecules. Consistent with cryoSEM images and temperature-dependent Raman spectral data, the ADI is dehydrated in more crystalline ice and hydrated in more glassy ice. The current investigation serves as a starting point for using more sensitive spectroscopic techniques for studying water-organics interactions at a much lower concentration and wider temperature range.

Phosphorus addition increases stability and complexity of co-occurrence network of soil microbes in an artificial Leymus chinensis grassland.

Introduction: Understanding the response of cross-domain co-occurrence networks of soil microorganisms to phosphorus stability and the resulting impacts is critical in ecosystems, but the underlying mechanism is unclear in artificial grassland ecosystems. Methods: In this study, the effects of four phosphorus concentrations, P0 (0 kg P ha-1), P1 (15.3 kg P ha-1), P2 (30.6 kg P ha-1), and P3 (45.9 kg P ha-1), on the cross-domain co-occurrence network of bacteria and fungi were investigated in an artificial Leymus chinensis grassland in an arid region. Results and discussion: The results of the present study showed that phosphorus addition significantly altered the stem number, biomass and plant height of the Leymus chinensis but had no significant effect on the soil bacterial or fungal alpha (ACE) diversity or beta diversity. The phosphorus treatments all increased the cross-domain co-occurrence network edge, node, proportion of positively correlated edges, edge density, average degree, proximity to centrality, and robustness and increased the complexity and stability of the bacterial-fungal cross-domain co-occurrence network after 3 years of continuous phosphorus addition. Among them, fungi (Ascomycota, Basidiomycota, Mortierellomycota and Glomeromycota) play important roles as keystone species in the co-occurrence network, and they are significantly associated with soil AN, AK and EC. Finally, the growth of Leymus chinensis was mainly due to the influence of the soil phosphorus content and AN. This study revealed the factors affecting the growth of Leymus chinense in artificial grasslands in arid areas and provided a theoretical basis for the construction of artificial grasslands.

Binding Strengths and Orientations in CO2 Adsorption on Cationic Scandium Oxides: Governing Factor Revealed by a Combined Infrared Spectroscopy and Theoretical Study.

Carbon dioxide (CO2) adsorption is a critical step to curbing carbon emissions from fossil fuel combustion. Among various options, transition metal oxides have received extensive attention as promising CO2 adsorbents due to their affordability and sustainability for large-scale use. Here, the nature of binding interactions between CO2 molecules and cationic scandium oxides of different sizes, i.e., ScO+, Sc2O2+, and Sc3O4+, is investigated by mass-selective infrared photodissociation spectroscopy combined with quantum chemical calculations. The well-accepted electrostatic considerations failed to provide explanations for the trend in the binding strengths and variations in the binding orientations between CO2 and metal sites of cationic scandium oxides. The importance of orbital interactions in the driving forces for CO2 adsorption on cationic scandium oxides was revealed by energy decomposition analyses. A molecular surface property, known as the local electron attachment energy, is introduced to elucidate the binding affinity and orientation-specific reactivity of cationic scandium oxides upon the CO2 attachment. This study not only reveals the governing factor in the binding behaviors of CO2 adsorption on cationic scandium oxides but also serves as an archetype for predicting and rationalizing favorable binding sites and orientations in extended surface-adsorbate systems.

Density Functional Theory Calculations on Fluorescence-Enhanced Mechanisms of the Optical Sensor for Zinc Ions, ADPA.

N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine (ADPA) as a specific ion sensor for Zn2+ has been widely applied. Although the photo-induced electron transfer (PET) mechanism was proposed previously, its fluorescence-enhanced effect still remains somewhat ambiguous, according to unknown influences of non-radiative energy decay pathways, such as intersystem crossing and internal conversion. Herein, a thorough study using density functional theory has been performed for low-lying electronic states of the ADPA monomer and hydrated ADPA-Zn2+ complex. Based on interfragment charge transfer analyses, we quantitatively calculated the amount of transferred electrons in the monomer and complex, providing solid evidences for the PET mechanism and in line with the conclusion of frontier molecular orbital analyses. Moreover, the ISC process of S1→T2 was confirmed to play a considerable role in the excitation energy relaxation process of the ADPA monomer, but this influence was significantly suppressed in the hydrated ADPA-Zn2+ complex. These results provide additional clues for the design of new metal ion-specific fluorescence probes.

Vibrational state-specific nonadiabatic photodissociation dynamics of OCS+ via A2Π1/2 (ν1 0 ν3) states.

The identification and analysis of quantum state-specific effects can significantly deepen our understanding of detailed photodissociation dynamics. Here, we report an experimental investigation on the vibrational state-mediated photodissociation of the OCS+ cation via the A2Π1/2 (ν1 0 ν3) states by using the velocity map ion imaging technique over the photolysis wavelength range of 263-294 nm. It was found that the electronically excited S+ product channel S+(2Du) + CO (X1Σ+) was significantly enhanced when the ν1 and ν3 vibrational modes were excited. Clear deviations in the branching ratios of the electronically excited S+ channel were observed when the vibrational modes ν1 and ν3 were selectively excited. The results reveal that vibrationally excited states play a vital role in influencing the nonadiabatic couplings in the photodissociation process.

In situ Raman spectral observation of succinimide intermediates in amyloid fibrillation kinetics.

Succinimide intermediates play the crucial role in the nucleation process for protein amyloid fibril formation, as they can usually induce a non-native conformation in a fraction of soluble proteins to render amyloidogenicity and neurotoxicity. Thus, in situ detection of succinimide intermediates during amyloid fibrillation kinetics is of considerable importance, albeit challenging, because these succinimides are generally unstable in physiological conditions. Here, we found an in situ Raman spectral fingerprint to trace the succinimide intermediates in amyloid fibril formation, wherein the carbonyl symmetric stretching of cyclic imide in the succinimide derivative is located at ca. 1790 cm-1. Using its intensity as an indicator of succinimide intermediates, we have in situ detected and unravelled the role of succinimide intermediates during the oligomer formation from the Bz-Asp-Gly-NH2 dipeptide or the amyloid fibrillation kinetics of lysozyme with thermal/acid treatment.

Carbon dioxide activation by discandium dioxide cations in the gas phase: a combined investigation of infrared photodissociation spectroscopy and DFT calculations.

We present a combined computational and experimental study of CO2 activation at the Sc2O2+ metal oxide ion center in the gas phase. Density functional theory calculations on the structures of [Sc2O2(CO2)n]+ (n = 1-4) ion-molecule complexes reveal a typical end-on binding motif as well as bidentate and tridentate carbonate-containing configurations. As the number of attached CO2 molecules increases, activated forms tend to dominate the isomeric populations. Distortion energies are unveiled to account for the conversion barriers from molecularly bound isomers to carbonate structures, and show a monotonically decreasing trend with successive CO2 ligand addition. The infrared photodissociation spectra of target ion-molecule complexes were recorded in the 2100-2500 cm-1 frequency region and interpreted by comparison with simulated IR spectra of low-lying isomers representing distinct configurations, demonstrating a high possibility of carbonate structure formation in current experiments.

A convenient switch design for high time resolution and energy resolution in ion velocity imaging.

Time-sliced velocity map imaging (VMI) has extensively been applied in photodissociation dynamics studies, thanks to its unique advantages, such as high energy resolution and no requirement of inverse Abel or Hankel transformations. However, its time resolution is generally insufficient for distinguishing adjacent m/z ions with a certain kinetic energy due to the overlapping of time-of-flight distributions. Herein, we have made a novel and convenient switch design for the common ion optics in three-dimensional (3D) VMI. By simply introducing two additional resistors out of the vacuum chamber, the strength ratio of the extraction and acceleration fields is easily changed from 3D VMI to two-dimensional (2D) VMI under optimized conditions, as well as a significant extension of free drift length, leading to a higher time resolution while maintaining the high energy resolution. As a result, 2D and 3D VMI can be quickly switched without breaking the vacuum and replacing the electrostatic plates.

Observation of inserted oxocarbonyl species in the tantalum cation-mediated activation of carbon dioxide dictated by two-state reactivity.

Reductive activation of carbon dioxide (CO2) has drawn increasing attention as an effective and convenient method to unlock this stable molecule, especially via transition metal-catalyzed reactions. Taking the [TaC4O8]+ ion-molecule complex formed in the laser ablation source as a representative, the reactivity of the tantalum metal cation towards CO2 molecules is explored using infrared photodissociation spectroscopy combined with quantum chemical calculations. The strong absorption in the carbonyl stretching region provides solid evidence for the insertion reactions into CO bonds by the tantalum cation. Two inserted oxocarbonyl products are identified based on the great agreement between the experimental results and simulated infrared spectra of energetically low-lying structures in the singlet and triplet states. The pivotal role of two-state reactivity in driving CO2 activation among three different spin states is rationalized by potential energy surface analysis. Our conclusion provides valuable insight into the intrinsic mechanisms of CO2 activation by the tantalum metal cation, highlighting the affinity of tantalum for CO bond insertion in addition to typical "end-on" binding configurations.

Hybrid Path Planning for Unmanned Surface Vehicles in Inland Rivers Based on Collision Avoidance Regulations.

In recent years, with the continuous advancement of the construction of the Yangtze River's intelligent waterway system, unmanned surface vehicles have been increasingly used in the river's inland waterways. This article proposes a hybrid path planning method that combines an improved A* algorithm with an improved model predictive control algorithm for the autonomous navigation of the "Jinghai-I" unmanned surface vehicle in inland rivers. To ensure global optimization, the heuristic function was refined in the A* algorithm. Additionally, constraints such as channel boundaries and courses were added to the cost function of A* and the planned path was smoothed to meet the collision avoidance regulations for inland rivers. The model predictive control algorithm incorporated a new path-deviation cost while imposing a cost constraint on the yaw angle, significantly minimizing the path-tracking error. Furthermore, the improved model predictive control algorithm took into account the requirements of rules in the cost function and adopted different collision avoidance parameters for different encounter scenarios, improving the rationality of local path planning. Finally, the proposed algorithm's effectiveness was verified through simulation experiments that closely approximated real-world navigation conditions.

Dependence of Intramolecular Hydrogen Bond on Conformational Flexibility in Linear Aminoalcohols.

Intramolecular hydrogen bonds (H-bonds) are abundant in physicochemical and biological processes. The strength of such interaction is governed by a subtle balance between conformational flexibility and steric effect that are often hard to predict. Herein, using linear aminoalcohols NH2(CH2)nOH (n = 2-5) as a model system, we demonstrated the dependence of intramolecular H-bond on the backbone chain length. With sensitive photoacoustic Raman spectroscopy (PARS), the gas-phase Raman spectra of aminoalcohols were measured in both N-H and O-H stretching regions at 298 and 338 K and explained with the aid of quantum chemistry calculations. For n = 2-4, two conformers corresponding to the O-H···N intramolecular H-bond and free OH were identified, whereas for n = 5, only the free-OH conformer was identified. Compared to free OH, a striking spectral dependence was observed for the intramolecular H-bonded conformer. According to the red shift of the OH-bonded band, the strongest intramolecular H-bond yields in n = 4, but the favorable chain length to form an intramolecular hydrogen bond at room temperature was observed in n = 3, which corresponds to a six-membered-ring in 3-aminopropanol. This is in good agreement with statistical analysis from the Cambridge Structural Database (CSD) that the intramolecular hydrogen bond is preferred when the six-membered ring is formed. Furthermore, combined with the calculated thermodynamic data at the MP2/aug-cc-pVTZ//M062X/6-311++G(d,p) level, the origin of decrease in intramolecular hydrogen-bond formation was ascribed to an unfavorable negative entropy contribution when the backbone chain is further getting longer, which results in the calculated Gibbs free energy optimum changing with increasing temperature from n = 4 (0-200 K) to n = 3 (200-400 K) and to n = 2 (above 400 K). These results will provide new insight into the nature of intramolecular hydrogen bonds at the molecular level and the application of intramolecular hydrogen bonds in rational drug design and supramolecular assembly.

Driving factors for decoupling water resources ecological footprint and economic growth in water-deficient cities dominated by agriculture.

To explore the key factors and specific thresholds of water resources limiting economic development, and to provide technical support for water resources management in cities dominated by agriculture similar to Zhangjiakou. We used the Tapio elastic decoupling method to quantitatively evaluate the decoupling relationship between the water resources ecological footprint (WEF) and economic growth. Then the logarithmic mean Divisia index (LMDI) and mathematical statistics are used to identify the key factors and threshold effects. The results show a significant decreasing trend in the WEF and obvious spatial differences in Zhangjiakou between 2006 and 2015, with agricultural ecological footprint dominating all districts and counties (77.54 ± 14.35%). The changes in technological effect are a contributing factor to the decoupling between the WEF and the economy in Zhangjiakou, while the economic effect is the main restricting factor. In particular, there is a high correlation between the WEF and the number of water-saving irrigation machines and the total power of agricultural machinery. According to the findings, for water-scarce cities such as Zhangjiakou, where agriculture is the primary focus, it is suggested that increasing the number of agricultural machinery can effectively alleviate the problem of water scarcity constraining economic development.

Efficient Red-to-Blue Triplet-Triplet Annihilation Upconversion Using the C70-Bodipy-Triphenylamine Triad as a Heavy-Atom-Free Triplet Photosensitizer.

Triplet-triplet annihilation upconversion (TTA-UC) with heavy-atom-free organic triplet photosensitizers has attracted extensive attention recently, however, the successful examples with absorption in red and first near-infrared (NIR-I, 650-900 nm) region are still insufficient. Herein, we conducted a new TTA-UC system of perylene using C70-bodipy-triphenylamine triad (C70-BDP-T) as the heavy-atom-free photosensitizer. Efficient red-to-blue (663 to 450 nm) TTA-UC was achieved in this system with an anti-Stokes shift of 0.88 eV and a quantum yield up to 5.2% (out of a 50% maximum) in deaerated toluene. Notably, this is the highest quantum yield to date in similar TTA-UC systems with heavy-atom-free organic photosensitizers. Using steady-state and transient absorption spectroscopy, together with cyclic voltammogram and quantum chemical calculations, photophysical and photochemical mechanisms were elucidated. Specifically, two triplet triads, C70-3BDP*-T and 3C70*-BDP-T, were produced efficiently upon photoexcitation, with lifetimes of 2.0 ± 0.1 and 32.2 ± 0.3 µs, respectively. Electron transfer and recombination mechanisms were confirmed to play crucial roles in the formation of these triplets, instead of intersystem crossing. Our results shed light on the superiority of fullerenes in the development of heavy-atom-free photosensitizers.

How generic is iodide-tagging photoelectron spectroscopy: An extended investigation on the Gly·X- (Gly = glycine, X = Cl or Br) complexes.

We report a joint negative ion photoelectron spectroscopy (NIPES) and quantum chemical computational study on glycine-chloride/bromide complexes (denoted Gly·X-, X = Cl/Br) in close comparison to the previously studied Gly·I- cluster ion. Combining experimental NIPE spectra and theoretical calculations, various Gly·X- complexes were found to adopt the same types of low-lying isomers, albeit with different relative energies. Despite more congested spectral profiles for Gly·Cl- and Gly·Br-, spectral assignments were accomplished with the guidance of the knowledge learned from Gly·I-, where a larger spin-orbit splitting of iodine afforded well-resolved, recognizable spectral peaks. Three canonical plus one zwitterionic isomer for Gly·Cl- and four canonical conformers for Gly·Br- were experimentally identified and characterized in contrast to the five canonical ones observed for Gly·I- under similar experimental conditions. Taken together, this study investigates both genericity and variations in binding patterns for the complexes composed of glycine and various halides, demonstrating that iodide-tagging is an effective spectroscopic means to unravel diverse ion-molecule binding motifs for cluster anions with congested spectral bands by substituting the respective ion with iodide.

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

Singlet oxygen (1O2) shows great potential for selective degradation of dyes in environmental remediation of wastewater. In this study, we showcased that 1O2 can be effectively generated from an anion complex composed of deprotonated hexafluoroisopropanol anion ([HFIP-H]‒) with hydroperoxyl radical (⋅HO2) via ultraviolet (UV) photodetachment. Electronic structure calculations and cryogenic negative ion photoelectron spectroscopy unveil critical proton transfer upon complex formation and electron ejection, effectively photoconverting prevalent triplet ground state 3O2 to long-lived excited 1O2, stabilized by nearby HFIP. Inspired by this spectroscopic study, a novel "photogeneration" strategy is proposed to produce 1O2 with the incorporation of atmospheric O2 and HFIP, acting as a catalyst. Conceptually, the designed catalytic cycle upon UV irradiation and electron injection is able to achieve different degradations of dye molecules in a controllable fashion from decolorization to complete mineralization, shedding new light on potential water purification.

Manganese Ion-Induced Amyloid Fibrillation Kinetics of Hen Egg White-Lysozyme in Thermal and Acidic Conditions.

As manganese ions (Mn2+) are identified as an environmental risk factor for neurodegenerative diseases, uncovering their action mechanism on protein amyloid fibril formation is crucial for related disease treatments. Herein, we performed a combined study of Raman spectroscopy, atomic force microscopy (AFM), thioflavin T (ThT) fluorescence, and UV-vis absorption spectroscopy assays, in which the distinctive effect of Mn2+ on the amyloid fibrillation kinetics of hen egg white-lysozyme (HEWL) was clarified at the molecular level. With thermal and acid treatments, the unfolding of protein tertiary structures is efficiently accelerated by Mn2+ to form oligomers, as indicated by two Raman markers for the Trp residues on protein side chains: the FWHM at 759 cm-1 and the I1340/I1360 ratio. Meanwhile, the inconsistent evolutionary kinetics of the two indicators, as well as AFM images and UV-vis absorption spectroscopy assays, validate the tendency of Mn2+ toward the formation of amorphous aggregates instead of amyloid fibrils. Moreover, Mn2+ plays an accelerator role in the secondary structure transition from α-helix to organized ß-sheet structures, as indicated by the N-Cα-C intensity at 933 cm-1 and the amide I position of Raman spectroscopy and ThT fluorescence assays. Notably, the more significant promotion effect of Mn2+ on the formation of amorphous aggregates provides credible clues to understand the fact that excess exposure to manganese is associated with neurological diseases.

Infrared photodissociation spectroscopy of mass-selected [TaO3(CO2)n]+ (n = 2-5) complexes in the gas phase.

We report a joint experimental and theoretical study on the structures of gas-phase [TaO3(CO2)n]+ (n = 2-5) ion-molecule complexes. Infrared photodissociation spectra of mass-selected [TaO3(CO2)n]+ complexes were recorded in the frequency region from 2200 to 2450 cm-1 and assigned through comparing with the simulated infrared spectra of energetically low-lying structures derived from quantum chemical calculations. With the increasing number of attached CO2 molecules, the larger clusters show significantly enhanced fragmentation efficiency and a strong band appears at around 2350 cm-1 near the free CO2 antisymmetric stretching vibration band, indicating only a small perturbation of CO2 molecules on the secondary solvation sphere while higher frequency bands corresponding to the core structure remain largely unaffected. A core structure [TaO3(CO2)3]+ is identified to which subsequent CO2 ligands are weakly attached and the most favorable cluster growth path is verified to proceed on the triplet potential energy surface higher in energy than that of ground states. Theoretical exploration reveals a two-state reactivity (TSR) scenario in which the energetically favored triplet transition state crosses over the singlet ground state to form a TaO3+ core ion, providing new information on the cluster formation correlated with the reactivity of tantalum metal oxides towards CO2.