NH Groups Research Articles

Thiol-based chemically modified carbon screen-printed electrode for simultaneous quantification of trace level Pb(II) and Cd(II).

Present work reports, the development of a novel electrochemical sensor based on a diazonium-coupling reaction and covalent attachment of the -NH2 group of cysteamine (Cyst) on screen-printed carbon electrode (SPCE), for simultaneous determination of Pb(II) and Cd(II). Initially, the in-situ generated 4-carboxyphenyl (4-CP) diazonium salt was electro-grafted to generate 4-CP/SPCE, followed by covalent bonding of terminal carboxylic group of 4-CP with -NH2 group of Cyst to give Cyst/4-CP/SPCE. The modified electrode showed an enhanced selectivity and sensitivity toward the quantification of Pb(II) and Cd(II) using square wave anodic stripping voltammetry (SWASV) without mutual interference. Under optimal experimental conditions, the newly designed sensor showed a wide linear range of 0.01µM to 0.7µM. The limit of detection (LOD) obtained was 0.882nM (0.09 ppb) and 0.65nM (0.134ppb) for Cd(II) and Pb(II), respectively. The modified SPCE exhibited good stability, selectivity, and reproducibility. Furthermore, the sensor was successfully applied for the determination of Pb(II) and Cd(II) ions in water samples which illustrated excellent recoveries in different spiked samples and the results were in line with the standard ICP-AES analysis.

Tracking the Dimensionality Transition from a Three Dimensional Single Crystal to a Two Dimensional Perovskite

AbstractThis work carefully studied the transition from 3D perovskite to 2D perovskite. Our system includes single crystals (SCs) of MAPbBr3, which were dipped in a solution of barrier molecules. Three monoammonium cations and one di‐ammonium cation were studied. Absorbance and cathodoluminescence were used to follow the formation of low‐dimensional perovskite on the SC surface. Quantitative nuclear magnetic resonance and scanning electron microscopy assist in quantitatively tracking the exchange process. We followed the barrier molecules′ concentration during the exchange process and their penetration depth into the 3D single crystal. The short aliphatic chain penetrates much farther into the crystal (ca. 450 μm) than the long aliphatic chain barrier molecule. In contrast, the process time is the opposite: the long aliphatic chain requires 5 days to achieve an equilibrium state compared with 15 days for the short aliphatic chain. Ab initio calculations indicate that the exchange process initiates due to the methylammonium vacancies on the surface, and the process is inhibited by the interactions between the −NH3 group and the PbBr2 planes. This work sheds light on the kinetics and thermodynamics of the transition from 3D to 2D perovskites, which is important for stabilizing the hybrid perovskites.

In-Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions.

Identification of molecules in complex natural matrices relies on matching the fragmentation spectra of ions under investigation and the spectra acquired for the corresponding analytical standards. Currently, there are many databases of experimentally measured tandem mass spectrometry spectra (such as NIST, MzCloud, and Metlin), and considerable progress has been made in the development of software for predicting tandem mass spectrometry fragments in silico using combinatorial, machine learning, and quantum chemistry approaches (such as MetFrag, CFM-ID, and QCxMS). However, the electrospray ionization molecules can be ionized at different sites (protonated or deprotonated), and the fragmentation spectra of such ions are different. Here, we are using the combination of the in-ESI source hydrogen/deuterium exchange reaction and MSn fragmentation for the investigation of the fragmentation pathways for different protomers of organic molecules. It is shown that the distribution of the deuterium in the fragment ions reflects the presence of different protomers. For several molecules, the distribution of deuterium was traced up to the MS5 level of fragmentation revealing many unusual and unexpected effects. For example, we investigated the loss of HF from the ciprofloxacin and norfloxacin ions and observed that for ions protonated at -COOH group, the eliminating hydrogen always comes from -NH group. When ions are protonated at another site, the elimination of hydrogen with a probability of 30% occurs from the -NH group, and with a probability of 70%, it originates from other sites on the molecule. Such effects were not described previously. Quantum chemical simulation was used for the verification of the protonated structures and simulation of the corresponding fragmentation spectra.

PEG-crosslinked O-carboxymethyl chitosan films with degradability and antibacterial activity for food packaging

This study developed a kind of PEG-crosslinked O-carboxymethyl chitosan (O-CMC–PEG) with various PEG content for food packaging. The crosslinking agent of isocyanate-terminated PEG was firstly synthesized by a simple condensation reaction between PEG and excess diisocyanate, then the crosslink between O-carboxymethyl chitosan (O-CMC) and crosslinking agent occurred under mild conditions to produce O-CMC–PEG with a crosslinked structure linked by urea bonds. FT-IR and 1H NMR techniques were utilized to confirm the chemical structures of the crosslinking agent and O-CMC–PEGs. Extensive research was conducted to investigate the impact of the PEG content (or crosslinking degree) on the physicochemical characteristics of the casted O-CMC–PEG films. The results illuminated that crosslinking and components compatibility could improve their tensile features and water vapor barrier performance, while high PEG content played the inverse effects due to the microphase separation between PEG and O-CMC segments. The in vitro degradation rate and water sensitivity primarily depended on the crosslinking degree in comparison with the PEG content. Furthermore, caused by the remaining –NH2 groups of O-CMC, the films demonstrated antibacterial activity against Escherichia coli and Staphylococcus aureus. When the PEG content was 6% (medium crosslinking degree), the prepared O-CMC–PEG−6% film possessed optimal tensile features, high water resistance, appropriate degradation rate, low water vapor transmission rate and fine broad-spectrum antibacterial capacity, manifesting a great potential for application in food packaging to extend the shelf life.

Tuning structural and electronic properties of metal-organic framework 5 by metal substitution and linker functionalization.

The chemical flexibility of metal-organic frameworks (MOFs) offers an ideal platform to tune structure and composition for specific applications, from gas sensing to catalysis and from photoelectric conversion to energy storage. This variability gives rise to a large configurational space that can be efficiently explored using high-throughput computational methods. In this work, we investigate from first principles the structural and electronic properties of MOF-5 variants obtained by replacing Zn with Be, Mg, Cd, Ca, Sr, and Ba and by functionalizing the originally H-passivated linkers with CH3, NO2, Cl, Br, NH2, OH, and COOH groups. To build and analyze the resulting 56 structures, we employ density-functional theory calculations embedded in an in-house developed library for automatized calculations. Our findings reveal that structural properties are mainly defined by metal atoms and large functional groups, which distort the lattice and modify coordination. The formation energy is largely influenced by functionalization and enhanced by COOH and OH groups, which promote the formation of hydrogen bonds. The charge distribution within the linker is especially influenced by functional groups with electron-withdrawing properties, while the metal nodes play a minor role. Likewise, the bandgap size is crucially determined by ligand functionalization. The smallest gaps are found with NH2 and OH groups, which introduce localized orbitals at the top of the valence band. This characteristic makes these functionalizations particularly promising for the design of MOF-5 variants with enhanced gas uptake and sensing properties.

High-Entropy Polymer Electrolytes Derived from Multivalent Polymeric Ligands for Solid-State Lithium Metal Batteries with Accelerated Li+ Transport.

Solid-state polymer-based electrolytes (SSPEs) exhibit great possibilities in realizing high-energy-density solid-state lithium metal batteries (SSLMBs). However, current SSPEs suffer from low ionic conductivity and unsatisfactory interfacial compatibility with metallic Li because of the high crystallinity of polymers and sluggish Li+ movement in SSPEs. Herein, differing from common strategies of copolymerization, a new strategy of constructing a high-entropy SSPE from multivariant polymeric ligands is proposed. As a protocol, poly(vinylidene fluoride-co-hexafluoropropylene) (PH) chains are grafted to the demoed polyethylene imine (PEI) with abundant -NH2 groups via a click-like reaction (HE-PEIgPHE). Compared to a PH-based SSPE, our HE-PEIgPHE shows a higher modulus (6.75 vs 5.18 MPa), a higher ionic conductivity (2.14 × 10-4 vs 1.03 × 10-4 S cm-1), and a higher Li+ transference number (0.55 vs 0.42). A Li|HE-PEIgPHE|Li cell exhibits a long lifetime (1500 h), and a Li|HE-PEIgPHE|LiFePO4 cell delivers an initial capacity of 160 mAh g-1 and a capacity retention of 98.7%, demonstrating the potential of our HE-PEIgPHE for the SSLMBs.

Cyclic Azahelicene Dimers ShowingBright Circularly Polarized Luminescence and Selective Fluoride Recognition.

Although helicenes are promising molecules, the synthetic difficulty and tediousness have often been problems, and only small amounts of optically pure helicenes have been obtained by using chiral HPLC in most cases. Herein, aza[7]helicenes or closed-aza[7]helicenes with(1R)-menthyl substituents were selectively synthesized via the intramolecular Scholl reaction, and the diastereomeric pairs were separated by silica gel column chromatography. The optically pure helicenes were further transformed into the corresponding cyclic dimers, and the chiroptical properties were investigated. The rigidp-frameworks of the dimers led to the high molar extinction coefficients and fluorescence quantum yields, while the twisted helicene moieties induced clear Cotton effects and CPLin the visible region,and thehighCPL brightness (BCPL) was achieved. Furthermore, the cyclic dimers were found to have the macrocyclic cavity with the two NH groups suitable for the selective binding of a fluoride anion, which induced significantly redshifted fluorescence and CPL in the red region.

Cyclic Azahelicene Dimers Showing Bright Circularly Polarized Luminescence and Selective Fluoride Recognition

Although helicenes are promising molecules, the synthetic difficulty and tediousness have often been problems, and only small amounts of optically pure helicenes have been obtained by using chiral HPLC in most cases. Herein, aza[7]helicenes or closed‐aza[7]helicenes with (1R)‐menthyl substituents were selectively synthesized via the intramolecular Scholl reaction, and the diastereomeric pairs were separated by silica gel column chromatography. The optically pure helicenes were further transformed into the corresponding cyclic dimers, and the chiroptical properties were investigated. The rigid p‐frameworks of the dimers led to the high molar extinction coefficients and fluorescence quantum yields, while the twisted helicene moieties induced clear Cotton effects and CPL in the visible region, and the high CPL brightness (BCPL) was achieved. Furthermore, the cyclic dimers were found to have the macrocyclic cavity with the two NH groups suitable for the selective binding of a fluoride anion, which induced significantly redshifted fluorescence and CPL in the red region.

Discovery of a New Polymorph of 5-Methoxy-1H-Indole-2-Carboxylic Acid: Characterization by X-Ray Diffraction, Infrared Spectroscopy, and DFT Calculations

This study presents a new 5-methoxy-1H-indole-2-carboxylic acid (MI2CA) polymorph investigated by single-crystal X-ray diffraction, infrared spectroscopy, and density functional theory (ωB97X-D) calculations employing two basis sets (6-31++G(d,p) and aug-cc-pVTZ). The compound crystallizes in the monoclinic system, space group P21/c (a = 4.0305(2) Å, b = 13.0346(6) Å, c = 17.2042(9) Å, β = 91.871(5)°, Z = 4). In the crystalline structure, the formation of cyclic dimers via double hydrogen bonds O−H⋯O between MI2CA molecules was observed. Interactions between the NH groups of the indole rings and the adjacent methoxy groups, as well as C–H⋯O contacts, significantly influence the spatial arrangement of molecules. The results from DFT calculations, including dimeric and trimeric structures, agree well with the experimental structural and spectroscopic data. Analysis of the infrared spectra confirms the conclusions drawn from X-ray diffraction studies and reveals differences between the IR spectra of the newly obtained polymorph and that reported earlier in the literature. This comprehensive study sheds some light on the MI2CA polymorphism and is important for a potential pharmacological applications of this compound.

Nonenzymatic dual glucose sensing on boronic acid modified zeolitic imidazolate framework-67 nanoparticles for diabetes management.

For early diabetes identification and management, the progression of an uncomplicated and exceedingly responsive glucose testing technology is crucial. In this study, we present a new sensor incorporating a composite of metal organic framework (MOF) based on cobalt, coated with boronic acid to facilitate selective glucose binding. Additionally, we successfully employed a highly sensitive electro-optical immunosensor for the detection of subtle changes in concentration of the diabetes biomarker glycated haemoglobin (HbA1c), using zeolitic imidazolate framework-67 (ZIF-67) coated with polydopamine which further modified with boronic acid. Utilizing the polymerization characteristics of dopamine and the NH2 groups, a bonding structure is formed between ZIF-67 and 4-carboxyphenylboronic acid. ZIF-67 composite served as an effective substrate for immobilising 4-carboxyphenylboronic acid binding agent, ensuring precise and highly selective glucose identification. The sensing response was evaluated through both electrochemical and optical methods, confirming its efficacy. Under optimized experimental condition, the ZIF-67 based sensor demonstrated a broad detection range of 50-500mg dL-1, a low limit of detection (LOD) of 9.87mg dL-1 and a high correlation coefficient of 0.98. Furthermore, the 4-carboxyphenylboronic acid-conjugated ZIF-67-based sensor platform exhibited remarkable sensitivity and selectivity in optical-based detection for glycated haemoglobin within the clinical range of 4.7-11.3%, achieving a LOD of 3.7%. These findings highlight the potential of the 4-carboxyphenylboronic acid-conjugated ZIF-67-based electro-optical sensor as a highly sensitive platform for diabetes detection.

Mechanistic Insights into the Excited-State Intramolecular Proton Transfer (ESIPT) Process of 2-(2-Aminophenyl)naphthalene.

The 2-(2-aminophenyl)naphthalene molecule attracted much attention due to excited-state intramolecular proton transfer (ESIPT) from an amino NH2 group to a carbon atom of an adjacent aromatic ring. The ESIPT mechanisms of 2-(2-aminophenyl)naphthalene are still unclear. Herein, the decay pathways of this molecule in vacuum were investigated by combining static electronic structure calculations and nonadiabatic dynamics simulations. The calculations indicated the existence of two stable structures (S0-1 and S0-2) in the S0 and S1 states. For the S0-1 isomer, upon excitation to the Franck-Condon point, the system relaxed to the S1 minimum quickly, and then there exist four decay pathways (two ESIPT ones and two decay channels with C atom pyramidalization). In the ESIPT decay pathways, the system encounters the S1S0-PT-1 or S1S0-PT-2 conical intersection, which funnels the system rapidly to the S0 state. In the other two pathways, the system de-excited from the S1 to the S0 state via the S1S0-1 or S1S0-2 conical intersection. For the S0-2 structure, the decay pathways were similar to those of S0-1. The dynamics simulations showed that 75 and 69% of trajectories experienced the two ESIPT conical intersections for the S0-1 and S0-2 structures, respectively. Our simulations showed that the lifetime of the S1 state of S0-1 (S0-2) is estimated to be 358 (400) fs. Notably, we not only found the detailed reaction mechanism of the system but also found that the different ground-state configurations of this system have little effect on the reaction mechanism in vacuum.

Phase transfer-assisted indium recovery from spent liquid crystal display panels and its extension in preparing indium-based electrocatalysts for CO2 reduction

Transforming discarded electronic devices into low-cost and high-efficiency catalysts presents a win–win approach to address the scarcity of rare resources and sustainable energy challenges. Herein, we report an effective strategy that combines an ethanol-mediated dodecylamine (DDA) phase transfer with hydrothermal methods for facilitating the facile synthesis of indium (In)-based nanomaterials from the leachates of liquid crystal display panels (LCDPs) toward high-efficiency electrochemical CO2 reduction reaction (eCO2RR). In this strategy, the rapid formation of coordinating compounds between the –NH2 group of DDA and metal ions facilitates the separation of In3+ cations from the acidic LCDPs leach solution by transferring them into an organic phase, which are then converted into InOOH nanoparticles with abundant oxygen vacancies (denoted as In-LCDPs and hereafter) through a low-temperature hydrothermal process. The eCO2RR evaluations confirm the superior electrocatalytic performance of the In-based nanoparticles produced from the LCDPs. In specific, within a broad potential range (−0.77 to −1.17 V vs RHE), the In-LCDPs show a Faradaic efficiency for formate (FEformate) of 85 %, with the highest FEformate of 90.23 % at −0.97 V vs RHE, which is comparable to the FEformate (93.8 % at −0.97 V vs RHE) of In-based catalyst prepared from pure In precursors using the same method. Further investigations reveal that the Sn and Al impurities have minimal impact on the catalytic performance of In-LCDPs, while the presence of Fe3+ impurities significantly enhance the production of hydrogen during the eCO2RR. This work might have provided a scalable pathway to transform LCDPs into value-added electrocatalysts for eCO2RR.

Synthesis and Biofunctional Properties of NaBr/H2O2‐Induced Brominated Uracil Derivatives

AbstractBromouracil derivatives are synthesized using an environmentally acceptable bromination protocol involving NaBr as a promoter. A minimum of 1.5 equivalent NaBr was required to reach the maximum yield. The reactions were conducted in an acidic medium in the presence of H2O2 under ambient conditions. We successfully synthesized ten novel 5‐bromouracil derivatives available in our laboratory and characterized them using various spectroscopic methods such as 1H‐NMR, 13C‐NMR, and SC‐XRD. All the derivatives are screened for anti‐bacterial activities against gram‐positive and gram‐negative bacteria. In particular, compounds 5‐bromo‐4‐chloro‐6‐methylpyrimidin‐2‐amine and 5‐bromo‐6‐chloropyrimidine‐2,4‐diamine exhibited prominent antibacterial activity against gram‐negative E. coli with IC50 values of ~9.8 and ~5.7 μg/mL. The structural‐activity relationship revealed that the presence of the −NH2 group in both the bromo derivatives affirms improving activity. Molecular docking studies also supported the experimental result and showed good binding energy of −4.4 (2 a) and −4.8 (2 b) kcal/mol against E. coli primase.

Stability of Iodine Species Trapped in Titanium-Based MOFs: MIL-125 and MIL-125_NH2.

Two titanium-based MOFs MIL-125 and MIL-125_NH2 are synthesized and characterized using high-temperature powder X-ray diffraction (PXRD), thermogravimetric analysis(TGA), N2 sorption, Fourier transformed infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet-visible spectroscopy (UV-Vis), and electron paramagnetic resonance (EPR). Stable up to 300°C, both compounds exhibited similar specific surface areas (SSA) values (1207 and 1099m2g-1 for MIL-125 and MIL-125_NH2, respectively). EPR signals of Ti3+ are observed in both, whith MIL-125_NH2 also showing ─NH2 ●+ signatures. Both MOFs efficiently adsorbed iodine in continuous gas flow over five days, with MIL-125 trapping 1.9g.g-1 and MIL-125_NH2 trapping 1.6g.g-1. MIL-125_NH2 exhibited faster adsorption kinetics due to its smaller band gap (2.5 against 3.6eV). In situ Raman spectroscopy conducted during iodine adsorption revealed signal evolution from "free" I2 to "perturbed" I2, and I3 -. TGA and in situ Raman desorption experiments showed that ─NH2 groups improved the stabilization of I3 - due to an electrostatic interaction with NH2 ●+BDC radicals. The Albery model indicated longer lifetimes for iodine desorption in I2@MIL-125_NH2, attributed to a rate-limiting step due to stronger interaction between the anionic iodine species and the ─NH2 ●+ radicals. This study underscores how MOFs with efficient charge separation and hole-stabilizer functional groups enhance iodine stability at higher temperatures.

A novel approach to l-tryptophan grafting on mesoporous MCM-41: A recoverable heterogeneous material for organocatalyzed benzo[N,N]-heterocyclic condensation

An unprecedented strategy has been developed to introduce l-tryptophan into MCM-41 by binding the indolic NH group of l-tryptophan to modified MCM-41, resulting in the creation of l-Tryp-N-pMCM-41. Initially, 3-Cl-pMCM-41 was prepared by modifying activated MCM-41 with 3-chloropropyltrimethoxysilane. Subsequently, the covalent attachment between the indolic NH group of l-tryptophan and 3-Cl-pMCM-41 was achieved using n‑butyl lithium in THF at -78 °C under an argon atmosphere. l-Tryp-N-pMCM-41 has been characterized by FT-IR, XRD, TGA, EDS, BET and nitrogen physisorption measurements. The organocatalytic performance of this chemically stable material was assessed in the synthesis of both symmetrical and unsymmetrical quinoxalines. The reaction involved the condensation of a series of aromatic 1,2-diamines with 1,2-diketones in methanol at room temperature. Overall, the organocatalytic reaction proceeded smoothly to afford the corresponding quinoxalines in moderate to excellent yields. Furthermore, the crystal structure of an unsymmetrical quinoxaline has been determined by single crystal X-ray diffraction. This metal-free procedure offers several noteworthy advantages, including the simplicity of the reaction, minimal catalyst usage, recyclability of the catalyst and environmentally friendly characteristics. Moreover, this green heterogeneous organocatalyst is a suitable candidate for preparing various valuable pharmaceutical compounds under ambient conditions avoiding the use of strong acids and without any possibility of metal contamination.

Multistimuli-responsive tetraphenylethene molecular switches displaying acid-sensing, photochromism, and metal ion detection properties

Aggregation-induced emission (AIE) smart materials with multiple stimulus responses have a wide range of applications. Here, a series of tetraphenylethylene (TPE) derivatives, TPEN1S3, TPEN2S2, TPEN3S1 were synthesized. The sensitivity of molecules to pH, UV light, and metal ions could be effectively tuned by modulating the ratio of amino to sulfonic acid groups. These TPE derivatives exhibited yellow emissions in aggregated state due to the AIE characteristics. Acidification conversion of the NH2 groups to NH3+ for three molecules induced the suppression of intramolecular charge transfer (ICT), which resulted in a 72–102 nm blue shift in the fluorescence emission. Solid powders of these compounds exhibited reversible protonation-deprotonation process induced by HCl/NH3·H2O vapor. TPEN1S3, TPEN2S2 and TPEN3S1 in solution could be photoactivated and emit blue fluorescence (ca. 482 nm, 475 nm, and 480 nm). Photocyclo-dehydrogenation reactions of compounds were triggered by the UV irradiation and the maximum cyclization ratios could reach 12%, 66%, and 50%, respectively. Protonation of NH2 group significantly enhanced the rate of the photocyclo-dehydrogenation reaction. Furthermore, the solid powders of protonated compounds displayed pronounced reversible photochromic properties due to the generation of cyclization intermediate. In addition, TPEN1S3, TPEN2S2, and TPEN3S1 exhibited responsiveness to a diverse range of metal ions. Specifically, the TPEN2S2 molecule functioned as a photo sensor for Li + ions with a blue shift in fluorescence emission. The limit of detection (LOD) value was 0.679 μM. These multiple stimuli-responsive AIE molecules hold significant potential for use in advanced photo-controlled patterning, encryption applications, and the detection of metal ions.

Proton exchange membranes based on sulfonated polybutylene fumarate: Preparation and characterization

AbstractBased on a novel unsaturated polyester, polybutylene fumarate (PBF), a series of sulfonated proton exchange membranes were prepared and characterized for direct methanol fuel cell application. In this work, PBF underwent sulfonation at different degrees, and the optimum degree of sulfonation (DS) was identified by assessing the hydrolytic stability. In the second step, an effective strategy to enhance the membranes' proton conductivity was adopted by the addition of the 2‐(1H‐Imidazol‐2‐yl) acetic acid (Im‐COOH) compound as a proton‐conducting agent to the sulfonated PBF (SPBF) matrix with the optimum DS. The results unveiled significant alterations in the physicochemical properties of PBF due to sulfonation, including an elevation in water uptake and the glass transition temperature (Tg), accompanied by the disappearance of the crystallinity within SPBF. In terms of electrochemical characteristics, the SPBF‐17.5 PEM demonstrated a proton conductivity of 3.36 × 10−3 S cm−1 and a methanol permeability of 1.068 × 10−7 cm2 s−1, yielding a selectivity of approximately 31,460 S s cm−3. Furthermore, the attractive interactions between SO3H and NH groups further elevated proton conductivity to 4.12 × 10−3 S cm−1, accompanied by a decrease in methanol permeability to 0.942 × 10−7 cm2 s−1, enhancing the selectivity parameter to 43,736 S s cm−3.

Why does urea not alter the vibrational spectroscopic signatures of water?

Usually, external solutes alter the local structural arrangement of the water hydrogen bond (H-bond) network. However, urea has a negligible effect on the local structure of water, irrespective of its concentration. In this work, we aim to find the microscopic origin of the inertness of urea toward water’s local structure by using theoretical isotope dilute IR spectroscopy. To get a microscopic resolution of different local environments, we investigate frequency distributions, population of structurally different ensembles, H-bond configurations, and H-bond strength. We find that urea has a negligible effect on the vibrational spectroscopic signatures of water. The solvation shell-wise decomposition of frequency distribution further reveals that the urea has almost zero perturbation to the local structure of any of its solvation shells. However, the frequency distribution of waters near the C=O group and NH2 group reveals a non-negligible impact by urea on water. The frequency distribution of the CO-region is red-shifted and narrower than the bulk water response, indicating a stronger H-bond and enhanced structural ordering of the waters in the CO-region; however, an opposite response is observed for the NH-region. The H-bond strength outcome further supplements this finding. We infer that the O-H oscillators in the CO-region and NH-region have non-negligible counteracting perturbation from the urea molecule. Yet, the overall response is free from any such effects. The insignificant populations and counteracting responses of these two ensembles play a major role.

Theoretical Spectroscopic Study of Normal Raman and Charge Transfer Surface-Enhanced Raman Scattering (SERS) Spectra of the Adsorbed l- and d-Cysteine on the Chiral Au34 and Ag4@Au30 Nanoclusters: Chirality Discrimination.

In this work, the discrimination of the enantiomers of cysteine (l- and d-CYS) using the chiral Au34 and Ag4@Au30 clusters was theoretically investigated in the gas phase and water. Two modes were considered for the interaction of each enantiomer with the clusters (via only its S atom or its S atom and NH2 group, simultaneously). The interaction energy (Eint) and adsorption energy (Ead) for the complexation of each enantiomer with the clusters for each interaction mode were calculated. Considering the calculated interaction energies, the interaction of d-CYS with Au34 is stronger than that of l-CYS with the same cluster. Also, it was observed that the substitution of the Au4 core of the Au34 cluster with the Ag4 cluster caused the increase of the interaction energy of l-CYS with the Ag4@Au30 cluster compared to the Au34 cluster, while the reverse trend was observed for d-CYS. Quantum theory of atoms in molecules (QTAIM) analysis was employed to calculate the interaction paths and their related bond critical points (BCPs) between the CYS enantiomers and the clusters to explain the difference between the interaction energy of the enantiomers with the clusters. The IR, normal Raman (NR), and surface-enhanced Raman scattering (SERS) spectra of the enantiomers interacting with the Au34 and Ag4@Au30 clusters were calculated, and the discrimination between l-CYS and d-CYS using the calculated spectra was explained. It was found that the discrimination of the enantiomers based on their interaction with the clusters is controlled by the charge transfer between the enantiomers and the clusters.

Ethidium benzoate methanol monosolvate.

In the title salt solvate (systematic name: 8-amino-5-ethyl-6-phenyl-phenanthridin-5-ium benzoate methanol monosolvate), C21H20N3 +·C6H5CO2 -·CH3OH, two ethidium cations, C21H20N3 +, dimerize about a twofold axis through π-π inter-actions [inter-centroid separation = 3.6137 (4) Å]. The benzoate anions are connected through hydrogen bonding with the -NH2 groups of the ethidium cations and the -OH group of the MeOH mol-ecule. The MeOH mol-ecule also accepts a hydrogen bond from the -NH2 group of the ethidium cation. The result is a one-dimensional hydrogen-bonded chain along the b-axis direction.