Spectroscopic Studies Research Articles

Synthesis, Stability, Meisenheimer Complex Formation, and Charge‐Transfer Properties of Ultra‐Electron‐Deficient Tetracyano‐Naphthalene Diimides

AbstractTetra‐cyano substituted naphthalene diimides (TCNDIs) with calculated LUMO of −5.2 eV, form one of the strongest electron‐acceptors known to date. However, the synthesis and isolation of this class of molecules remain challenging due to its reactivity emanating from its ultra‐electron‐deficiency. Herein we have established an improved synthetic methodology of TCNDIs with cost‐effective reagents and circumventing metallic catalysts. The synthesis is amenable to TCNDIs with the shortest axial alkyl groups, i. e., methyl group and also longer alkyl chains. We also gained insight on how axial alkyl chain lengths influence electron‐deficiency, Meisenheimer complex formation, reactivity, and charge‐transfer of TCNDIs from computation, spectroscopy, and electrochemical studies. The TCNDIs with Me/Et axial groups were found to be more susceptible to moist solvents vis‐à‐vis the TCNDIs with longer alkyl groups. The single crystal structures of the TCNDIs show infinitely π‐stacked structure, and a new C=O ⋅ ⋅ ⋅ C≡N or C≡N ⋅ ⋅ ⋅ π motif is discerned. Finally, toluene‐mediated charge‐transfer properties of TCNDIs in the single crystals as well as in solution have been examined.

Symmetry‐breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution

AbstractThe current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high‐performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry‐breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT‐1SO. The asymmetric structure of BBTT‐1SO proved beneficial for increasing multiple moment and polarizability. BBTT‐1SO‐containing polymers showed higher efficiencies for hydrogen evolution than their DBS‐containing counterparts by up to 166 %. PBBTT‐1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g−1 h−1 and an apparent quantum yield of 27.5 % at 500 nm. Transient spectroscopic studies indicated that the BBTT‐1SO‐based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT‐1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water‐PBBTT‐1SO polymer interactions in salt‐containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high‐performance photocatalysts for hydrogen evolution.

Symmetry-breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution.

The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high-performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry-breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT-1SO. The asymmetric structure of BBTT-1SO proved beneficial for increasing multiple moment and polarizability. BBTT-1SO-containing polymers showed higher efficiencies for hydrogen evolution than their DBS-containing counterparts by up to 166 %. PBBTT-1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g-1 h-1 and an apparent quantum yield of 27.5 % at 500 nm. Transient spectroscopic studies indicated that the BBTT-1SO-based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT-1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water-PBBTT-1SO polymer interactions in salt-containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high-performance photocatalysts for hydrogen evolution.

4‐Methyltetrahydropyran: A Versatile Alternative Solvent for the Preparation of Chiral BINOL Catalysts and the Asymmetric Alkylation of Aldehydes

AbstractWe herein report that the highly hydrophobic ether 4‐MeTHP constitutes a promising resource for the development of sustainable synthetic methodologies grounded on the use of organometallic reagents. The beneficial effects of 4‐MeTHP as reaction medium are illustrated in the organolithium‐promoted anionic ortho‐Fries rearrangement of 1,1’‐bi‐2‐naphthol (BINOL)‐based carbamates under bench‐type conditions. The use of 4‐MeTHP induces a remarkable and unexpected stability of the organolithiums species, enabling the efficient preparation of chiral (bis)carboxamide catalysts. Furthermore, superior performances of 4‐MeTHP than other environmentally responsible solvents are observed using the synthesized BINOL catalysts in the asymmetric addition of organozinc reagents to aldehydes. Spectroscopic studies in solution suggest that 4‐MeTHP plays a key role in these reactions by inducing the preferential formation of a reactive monomeric dinuclear complex. This methodology allows for the asymmetric assembly of enantioenriched secondary alcohols in good yields and high stereoselectivity, working at 0 °C and under air.

Impact of ASL Exposure on Spoken Phonemic Discrimination in Adult CI Users: A Functional Near-Infrared Spectroscopy Study

Abstract We examined the impact of exposure to a signed language (American Sign Language, or ASL) at different ages on the neural systems that support spoken language phonemic discrimination in deaf individuals with cochlear implants (CIs). Deaf CI users (N = 18, age = 18–24 yrs) who were exposed to a signed language at different ages and hearing individuals (N = 18, age = 18–21 yrs) completed a phonemic discrimination task in a spoken native (English) and non-native (Hindi) language while undergoing functional near-infrared spectroscopy neuroimaging. Behaviorally, deaf CI users who received a CI early versus later in life showed better English phonemic discrimination, albeit phonemic discrimination was poor relative to hearing individuals. Importantly, the age of exposure to ASL was not related to phonemic discrimination. Neurally, early-life language exposure, irrespective of modality, was associated with greater neural activation of left-hemisphere language areas critically involved in phonological processing during the phonemic discrimination task in deaf CI users. In particular, early exposure to ASL was associated with increased activation in the left hemisphere’s classic language regions for native versus non-native language phonemic contrasts for deaf CI users who received a CI later in life. For deaf CI users who received a CI early in life, the age of exposure to ASL was not related to neural activation during phonemic discrimination. Together, the findings suggest that early signed language exposure does not negatively impact spoken language processing in deaf CI users, but may instead potentially offset the negative effects of language deprivation that deaf children without any signed language exposure experience prior to implantation. This empirical evidence aligns with and lends support to recent perspectives regarding the impact of ASL exposure in the context of CI usage.

Quasi-Podands with 1,2,3-Triazole Rings from Bile Acid Derivatives: Synthesis, and Spectroscopic and Theoretical Studies.

An innovative approach to producing derivatives of bile acids has been devised, utilizing the principles of "click" chemistry. By employing intermolecular [3 + 2] cycloaddition between the newly developed acyl propiolic esters of bile acids and the azide groups of 1,3,5-tris(azidomethyl)benzene, a novel class of quasi-podands featuring 1,2,3-triazole rings has been synthesized. Identifying and characterizing these six compounds involved comprehensive analysis through spectral techniques (1H NMR, 13C NMR, and FT-IR), mass spectrometry, and the PM5 semiempirical method. The synthesized compounds' pharmacotherapeutic potential has been evaluated, employing the Prediction of Activity Spectra for Substances (PASS) methodology. Additionally, molecular docking was performed for all molecules.

2,6-Bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine: Effects of the Peripheral Aliphatic Side Chain on the Coordination of Actinides(III) and Lanthanides(III).

To improve our understanding of the interaction mechanism in trivalent lanthanide and actinide complexes, studies with structurally different hard and soft donor ligands are of great interest. For that reason, the coordination chemistry of An(III) and Ln(III) with 2,6-bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine (C4-BPP) has been explored. Time-resolved laser fluorescence spectroscopy (TRLFS) studies have revealed the formation of [Cm(C4-BPP)n]3+ (n = 1-3) (log β1' = 7.2 ± 0.4, log β2' = 10.1 ± 0.5, and log β3' = 11.8 ± 0.6) and [Eu(C4-BPP)m]3+ (m = 1-2) (log β1' = 4.9 ± 0.2 and log β2' = 8.0 ± 0.4). The absence of the [Eu(C4-BPP)3]3+ complex shows a more favorable complexation of Cm(III) over that of Eu(III). Additionally, complementary NMR measurements have been conducted to examine the M(III)-N bond in Ln(III) and Am(III) C4-BPP complexes. 15N NMR data have revealed notable differences in the chemical shifts of the coordinating nitrogen atoms between the Am(III) and Ln(III) complexes. In the Am(III) complex, the coordinating nitrogen atoms have shown a shift by 260 ppm, indicating a higher fraction of covalent bonding in the Am(III)-N bond compared with the Ln(III)-N bond. This observation aligns excellently with the differences in the stability constants obtained from TRLFS studies.

Exploring the Interfacial Hydrogen Transfer between Pt and the Siliceous Framework and Its Promotional Effect on the Isotope Catalytic Exchange.

Interfacial hydrogen transfer between metal particles and catalyst supports is a ubiquitous phenomenon in heterogeneous catalysis, and this occurrence on reducible supports has been established, yet controversies remain about how hydrogen transfer can take place on nonreducible supports, such as silica. Herein, highly dispersed Pt clusters supported on a series of porous silica materials with zeolitic or/and amorphous frameworks were prepared to interrogate the nature of hydrogen transfer and its promotional effect on H2-HDO isotope catalytic exchange. The formation of zeolitic frameworks upon these porous silica supports by hydrothermal crystallization greatly promotes the interfacial hydrogen bidirectional migration between metal clusters and supports. Benefiting from this transfer effect, the isotope exchange rate is enhanced by 10 times compared to that on the amorphous counterpart (e.g., Pt/SBA-15). In situ spectroscopic and theoretical studies suggest that the defective silanols formed within the zeolite framework serve as the reactive sites to bind HDO or H2O by hydrogen bonds. Under the electrostatic attraction interaction, the D of hydrogen-bonded HDO scrambles to the Pt site and the dissociated H on Pt simultaneously spills back to the electronegative oxygen atom of adsorbed water to attain H-D isotope exchange with an energy barrier of 0.43 eV. The reverse spillover D on Pt combines with the other H on Pt to form HD in the effluent. We anticipate that these findings are able to improve our understanding of hydrogen transfer between metal and silica supports and favor the catalyst design for the hydrogen-involving reaction.

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Photolysis is an attractive method in organic synthesis to produce free radicals through direct bond cleavage. However, in this method, specific irradiation wavelengths of light have been considered indispensable for excitation through S0–Sn or S0–Tn transitions. Here we report the photoinduced homolysis of electronegative interelement bonds using light at wavelengths much longer than theoretically and spectroscopically predicted for the S0–Sn or S0–Tn transitions. This long-wavelength photolysis proceeds in N–Cl, N–F, and O–Cl bonds at room temperature under blue, green, and red LED irradiation, initiating diverse radical reactions. Through experimental, spectroscopic, and computational studies, we propose that this “hidden” absorption is accessible via electronic excitations from naturally occurring vibrationally excited ground states to unbonded excited states and is due to the electron-pair repulsion between electronegative atoms.

Microwave Assisted Fast Synthesis of a Donor‐Acceptor COF Towards Photooxidative Amidation Catalysis

AbstractThe synthesis of covalent organic frameworks (COFs) at bulk scale require robust, straightforward, and cost‐effective techniques. However, the traditional solvothermal synthetic methods of COFs suffer low scalability as well as requirement of sensitive reaction environment and multiday reaction time (2–10 days) which greatly restricts their practical application. Here, we report microwave assisted rapid and optimized synthesis of a donor‐acceptor (D−A) based highly crystalline COF, TzPm‐COF in second (10 sec) to minute (10 min) time scale. With increasing the reaction time from seconds to minutes crystallinity, porosity and morphological changes are observed for TzPm‐COF. Owing to visible range light absorption, suitable band alignment, and low exciton binding energy (Eb=64.6 meV), TzPm‐COF can efficaciously produce superoxide radical anion (O2⋅−) after activating molecular oxygen (O2) which eventually drives aerobic photooxidative amidation reaction with high recyclability. This photocatalytic approach works well with a variety of substituted aromatic aldehydes having electron‐withdrawing or donating groups and cyclic, acyclic, primary or secondary amines with moderate to high yield. Furthermore, catalytic mechanism was established by monitoring the real‐time reaction progress through in situ diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) study.

Microwave Assisted Fast Synthesis of a Donor-Acceptor COF Towards Photooxidative Amidation Catalysis.

The synthesis of covalent organic frameworks (COFs) at bulk scale require robust, straightforward, and cost-effective techniques. However, the traditional solvothermal synthetic methods of COFs suffer low scalability as well as requirement of sensitive reaction environment and multiday reaction time (2-10 days) which greatly restricts their practical application. Here, we report microwave assisted rapid and optimized synthesis of a donor-acceptor (D-A) based highly crystalline COF, TzPm-COF in second (10 sec) to minute (10 min) time scale. With increasing the reaction time from seconds to minutes crystallinity, porosity and morphological changes are observed for TzPm-COF. Owing to visible range light absorption, suitable band alignment, and low exciton binding energy (Eb=64.6 meV), TzPm-COF can efficaciously produce superoxide radical anion (O2⋅-) after activating molecular oxygen (O2) which eventually drives aerobic photooxidative amidation reaction with high recyclability. This photocatalytic approach works well with a variety of substituted aromatic aldehydes having electron-withdrawing or donating groups and cyclic, acyclic, primary or secondary amines with moderate to high yield. Furthermore, catalytic mechanism was established by monitoring the real-time reaction progress through in situ diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) study.

Fe-N co-doped carbon nanofibers with Fe3C decoration for water activation induced oxygen reduction reaction

Abstract Proton activity at the electrified interface is central to the kinetics of proton-coupled electron transfer (PCET) reactions in electrocatalytic oxygen reduction reaction (ORR). Here, we construct an efficient Fe3C water activation site in Fe-N co-doped carbon nanofibers (Fe3C-Fe1/CNT) using an electrospinning-pyrolysis-etching strategy to improve interfacial hydrogen bonding interactions with oxygen intermediates during ORR. In situ Fourier transform infrared spectroscopy and density functional theory studies identified delocalized electrons as key to water activation kinetics. Specifically, the strong electronic perturbation of the Fe–N4 sites by Fe3C disrupts the symmetric electron density distribution, allowing more free electrons to activate the dissociation of interfacial water, thereby promoting hydrogen bond formation. This process ultimately controls the PCET kinetics for enhanced ORR. The Fe3C-Fe1/CNT catalyst demonstrates a half-wave potential of 0.83 V in acidic media and 0.91 V in alkaline media, along with strong performance in H2-O2 fuel cells and Al-air batteries.

Visible Light Induced Halogen Bond Assisted Friedel‐Crafts Reaction of Indole and Chalcones

AbstractThe use of halogen bonding interactions as an alternative to acid and metal catalysts for substrate activation has gained popularity in recent years. In this work we demonstrate a halogen bond assisted activation of chalcones under visible light irradiation for the Friedel‐Crafts reaction with indole to yield β‐indolylketones. The simple and scalable protocol uses the readily available CBr4 as halogen bond catalyst. The targets are produced in 31–94% of yield with excellent functional group tolerance. The proposed mechanism of the reaction is supported by UV‐vis, fluorescence, and NMR spectroscopic studies. Further it is demonstrated that the β‐indolylketones can be oxidised to indole substituted α, β‐unsaturated ketones by DDQ or cyclized to thieno[2,3‐b]indoles in the presence of elemental sulfur and base.

Tailoring the Ni-O Microenvironment in Amorphous-Dominated Highly Active and Stable Zn/NiO for Hydrogen Sulfide Detection.

Amorphous metal oxide semiconductor (MOS) materials are endowed with great promise to modulate electronic structures for gas-sensing performance improvement. However, the elevated-temperature requirement of gas sensors severely impedes the application of amorphous materials due to their low thermal stability. Here, a cationic-assisted strategy to tailor the Ni-O microenvironment in an amorphous-dominated Zn/NiO heterogeneous structure with high thermal stability was developed. It was found that 6 mol % Zn incorporation into amorphous NiO can effectively preserve the amorphous-dominated NiO phase even at high temperature. After calcination, the amorphous oxide can only be converted to crystals partly thus leading to the formation of amorphous/crystalline compounds, and the content of the amorphous phase can be adjusted by changing the calcination temperature. This amorphous/crystalline configuration can induce more electron transfer from Ni to Zn species, leading to the formation of active Niδ+ (δ>2) centers. Ex situ XPS and in situ Raman spectroscopy studies proved that the generated Niδ+ species pronouncedly promote the electron transfer during the H2S adsorption process. The amorphous/crystalline-6 mol % Zn/NiO sensor exhibits exceptional hydrogen sulfide response (2 ppm, 3.23), outstanding repeatability (as long as 5 weeks), and low limit of detection (as low as 50 ppb), surpassing most reported nickel-based gas sensors such as the crystal nickel oxide prepared in this work. The response and detection limit of the latter is only (2 ppm, 1.89) and (0.05 ppm) respectively. Our work thus opens up more opportunities for fundamental understanding and modulating of highly active amorphous sensing materials.

Implications for the Hydrogenation of Propyne and Propene with Parahydrogen due to thein situTransformation of Rh2C to Rh0/C.

NMR spectroscopy studies using parahydrogen-induced polarization have previously established the existence of the pairwise hydrogen addition route in the hydrogenation of unsaturated hydrocarbons over heterogeneous catalysts, including those based on rhodium (Rh0). This pathway requires the incorporation of both hydrogen atoms from one hydrogen molecule to the same product molecule. However, the underlying mechanism for such pairwise hydrogen addition must be better understood. The involvement of carbon, either in the form of carbonaceous deposits on the surface of a catalyst or as a metal carbide phase, is known to modify catalytic properties significantly and thus could also affect the pairwise hydrogen addition route. Here, we explored carbon's role by studying the hydrogenation of propene and propyne with parahydrogen on a Rh2C catalyst and comparing the results with those for a Rh0/C catalyst obtained from Rh2C via H2 pretreatment. While the catalysts Rh2C and Rh0/C differ notably in the rate of conversion of parahydrogen to normal hydrogen as well as in terms of hydrogenation activity, our findings suggest that the carbide phase does not play a significant role in the pairwise H2 addition route on rhodium catalysts.

Delayed cerebrovascular reactivity in individuals with spinal cord injury in the right inferior parietal lobe: a breath-hold functional near-infrared spectroscopy study.

Cerebrovascular reactivity (CVR) reflects the ability of blood vessels to dilate or constrict in response to a vasoactive stimulus, and allows researchers to assess the brain's vascular health. Individuals with spinal cord injury (SCI) are at an increased risk for autonomic dysfunction in addition to cognitive impairments, which have been linked to a decline in CVR; however, there is currently a lack of brain-imaging studies that investigate how CVR is altered after SCI. In this study, we used a breath-holding hypercapnic stimulus and functional near-infrared spectroscopy (fNIRS) to investigate CVR alterations in individuals with SCI (n = 20, 14M, 6F, mean age = 46.3 ± 10.2 years) as compared to age- and sex-matched able-bodied (AB) controls (n = 25, 19M, 6F, mean age = 43.2 ± 12.28 years). CVR was evaluated by its amplitude and delay components separately by using principal component analysis and cross-correlation analysis, respectively. We observed significantly delayed CVR in the right inferior parietal lobe in individuals with SCI compared to AB controls (linear mixed-effects model, fixed-effects estimate = 6.565, Satterthwaite's t-test, t = 2.663, p = 0.008), while the amplitude of CVR was not significantly different. The average CVR delay in the SCI group in the right inferior parietal lobe was 14.21 s (sd: 6.60 s), and for the AB group, the average delay in the right inferior parietal lobe was 7.08 s (sd: 7.39 s). CVR delays were also associated with the duration since injury in individuals with SCI, in which a longer duration since injury was associated with a shortened delay in CVR in the right inferior parietal region (Pearson's r-correlation, r = -0.59, p = 0.04). This study shows that fNIRS can be used to quantify changes in CVR in individuals with SCI, and may be further used in rehabilitative settings to monitor the cerebrovascular health of individuals with SCI.

Spectroscopic studies under properties of chlorpromazine conjugated to gold nanoparticles

Scientific studies have demonstrated that conjugates of anticancer drugs with metal nanoparticles (MeNPs) lead to a more effective deactivation of tumor cells compared to free drugs. Similarly, it has been established that conjugates of antibiotics with MeNPs exhibit higher biocidal activity against bacteria than their unbound counterparts. However, limited information is available regarding conjugates formed from drugs other than anticancer and antibiotics. Therefore, our research aims to develop synthesis methods for conjugates of chlorpromazine (CPZ), a neuroleptic, with gold nanoparticles (AuNPs). CPZ-AuNP conjugates were prepared through a ligand exchange reaction conducted on the surface of quasi-spherical, negatively charged citrate-stabilized TC-AuNPs with an average size of 55 ± 5 nm. UV–vis spectroscopy was employed to determine the stability range of the conjugates under controlled conditions of pH and ionic strength. Based on electrokinetic measurements, it was observed that the zeta potential of CPZ-AuNP conjugates strongly depends on the amount of CPZ adsorbed on the TC-AuNP surface. Additionally, the conjugates exhibited an isoelectric point at pH 8.8. Surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) were employed to elucidate the adsorption structure of CPZ on TC-AuNPs. The interpretation of the spectra was conducted based on the Raman and FTIR spectra of CPZ, along with calculations performed using Density Functional Theory (DFT). The results indicated that CPZ primarily interacts with the TC-AuNP surface through the angularly oriented phenothiazine ring and the propylene bridge. Furthermore, it was demonstrated that the C-N-C fragment is perpendicular to the surface of the TC-AuNP with which it interacts. The findings from this analysis suggest the potential for further research on the use of these conjugates in biomedical applications.

Liposome‐Based Delivery of a Bis‐benzimidazole Derivative to Duplex DNA: A Spectroscopic Study

AbstractDue to the immense pharmacological significance, the interaction of small molecules with liposome and the exact knowledge of their binding location and distribution within the lipid bilayer of liposome is an active field of biophysical research. Here, we have studied the binding interaction of H33258 with DPPC liposome, a model biological membrane. From the steady‐state fluorescence spectroscopy it was revealed that H33258 bounded to DPPC liposome and the estimated binding constant value was 2.5×102 M−1. It was also revealed that the H33258 essentially partitioned within the lipid bilayer of DPPC liposome. Moreover, from steady‐state fluorescence, time‐resolved lifetime, time‐resolved anisotropy and ITC studies it was established that the probe molecules were sequestrated from the lipid bilayer and bounded to a duplex DNA structure. Our results on the binding consequences of H33258 with liposome will aid development of a simple and safe strategy to deliver drugs to the target sites using liposome, endogenously.

Effect of electrophoretic deposition for selective detection of Pb2+ ions using nitrogen and sulphur-doped reduced graphene oxide

Lead is very hazardous, as it is present in environmental samples, and it causes severe health problems affecting neurological, cardiac, genital, and mental illnesses owing to exposure to even a trace amount. The achievement of selective detection of Pb2+ ions is challenging due to interfering relevant metal ions. Hence, in this work, we have synthesized the Nitrogen and Sulphur N and S-doped reduced graphene oxide (NS-rGO) and fabricated it using electrophoretic deposition (EPD) in glassy carbon electrode (GCE) and Bi film deposition (Bi/EPD-NS-rGO/GCE) for selective detection of Pb2+ ions. The synthesized materials were characterized to confirm their functionalities, elemental analysis, and morphology. Further, the electrochemical behaviours were also carried out through Cyclic Voltammetry (CV) and Electrochemical Impedimetric spectroscopy (EIS) studies. The above-modified electrodes were utilized for selective detection of Pb2+ in the presence of Cd2+ ionsusing the differential pulse anodic stripping voltammetry (DPASV) method. The electrode modified with NS-rGO using the EPD method, along with a thin film of Bi that was electrodeposited, has better and more selective catalytic activity for sensing Pb2+ ions. The linear working response was found to be in the range of 100–2200 nM with a limit of detection (LOD) of 0.180 nM and verified as 144 times lower than the recommended level (26 nM) by World Health Organization (WHO) and United States Environmental Protection Agency (USEPA). The developed sensor was further applied to the selective detection of Pb2+ ions in tap water and river water, and it shows good recovery. The Bi/EPD-NS-rGO/GCE will explore a new pathway for the simple and selective detection of Pb2+ ions.

Investigation of spin excitations and charge order in bulk crystals of the infinite-layer nickelate LaNiO2

Recent x-ray spectroscopic studies have revealed spin excitations and charge density waves in thin films of infinite-layer (IL) nickelates. However, clarifying whether the origin of these phenomena is intrinsic to the material class or attributable to impurity phases in the films has presented a major challenge. Here we utilize topotactic methods to synthesize bulk crystals of the IL nickelate LaNiO2 with crystallographically oriented surfaces. We examine these crystals using resonant inelastic x-ray scattering (RIXS) at the Ni L3-edge to elucidate the spin and charge correlations in the bulk of the material. While we detect the presence of prominent spin excitations in the crystals, fingerprints of charge order are absent at the ordering vectors identified in previous thin-film studies. These results contribute to the understanding of the bulk properties of LaNiO2 and establish topotactically synthesized crystals as viable complementary specimens for spectroscopic investigations. Published by the American Physical Society 2024