Spectroscopic Characterization Research Articles

Exploring cocrystals and polymorphism in pharmaceutical science: A comprehensive review

The pharmaceutical industry has been working hard in recent years to find ways to control polymorphism, which involves many solid drug forms due to their various physical and chemical characteristics. Creating cocrystals and salts of active pharmaceutical ingredients (APIs) is one potential research direction. These substances have drawn a lot of attention because they can improve crucial pharmacological features without reducing therapeutic efficacy. It is significant to note that not all compounds having multiple hydrogen bond donor/acceptor groups and polymorphism properties will form cocrystals; this behavior varies. Pharmaceutical firms and researchers alter APIs, frequently by generating cocrystals, salts, or polymorphs. This review discusses analytical approaches for solids drug forms such as diffraction, spectroscopy, thermal analysis, and pharmaceutical characterization. These techniques enable us to investigate solid APIs thoroughly, from their bulk characteristics to their molecular composition. They offer vital details regarding the composition, attributes, purity, and probable changes of the substance. These technologies are also useful for continuous monitoring and analysis of drug development physical procedures.

Tuning Lubrication Performance of Phase‐changing Emulsion‐filled Gels by Sugar alcohols

Lubrication by hydrogels is proving to be an emerging area in colloid science. Although oil‐driven friction reduction is predominant in literature, emulsion gel‐based lubrication has attracted very little attention to date. We hypothesize that an interplay of viscolelasticity and oil volume fraction may modulate lubricity of emulsion‐filled gels. Herein, phase‐change gelatin‐based emulsion‐filled gels with different sugar alcohol and oil droplet concentrations (0‐30 wt%) were tested for their lubrication performance. The rheological and tribological tests were analysed in conjunction with spectroscopic and structural characterizations in order to reveal structure‐function relationship. Structural characterizations demonstrated that hydrogen bonding was enhanced in pure gelatin gels with the increase of sugar alcohol (glycerol)‐replacement time, which enhanced the storage modulus (G') of the gel networks. Emulsified droplets served as active fillers further strengthening the G’ and strikingly the presence of glycerol reduced the thermo‐responsiveness of the emulsion‐filled gels. Emulsion‐filled gels containing sugar alcohols, irrespective of their type, can greatly reduce the friction coefficients (μ) between hydrophobic surfaces in the boundary and mixed regimes versus the systems without sugar alcohols. In the hydrodynamic regime, the friction coefficient of the system was proportional to the second plateau shear viscosity, regulated by the oil content.This article is protected by copyright. All rights reserved.

Probing the Origin of Overpotential for Sodium–Oxygen Batteries with Distribution of Relaxation Time

Sodium‐oxygen batteries are emerging as new battery systems. Deep understanding of the origin of overpotential and the kinetic process in sodium‐oxygen batteries remain challenging yet critical. We apply a method of distribution of relaxation time (DRT) to decipher the electrochemical impedance spectroscopy (EIS), allowing us to monitor the changes of different kinetic processes during the discharging and charging. The origin of the overpotential in a battery was further comprehensively investigated combining DRT analysis with differential electrochemical mass spectrometry, Raman and other characterizations. Overpotential is found to primarily stem from oxygen mass transport during discharging, and from poor solid‐solid contact at the electrode surface during charging. Our work demonstrates the study of kinetic processes using DRT analysis, and suggests effective ways to improve the performances of sodium‐oxygen batteries.

Correlating semiconductor nanoparticle architecture and applicability for the controlled encoding of luminescent polymer microparticles

Luminophore stained micro- and nanobeads made from organic polymers like polystyrene (PS) are broadly used in the life and material sciences as luminescent reporters, for bead-based assays, sensor arrays, printable barcodes, security inks, and the calibration of fluorescence microscopes and flow cytometers. Initially mostly prepared with organic dyes, meanwhile luminescent core/shell nanoparticles (NPs) like spherical semiconductor quantum dots (QDs) are increasingly employed for bead encoding. This is related to their narrower emission spectra, tuneability of emission color, broad wavelength excitability, and better photostability. However, correlations between particle architecture, morphology, and photoluminescence (PL) of the luminescent nanocrystals used for encoding and the optical properties of the NP-stained beads have been rarely explored. This encouraged us to perform a screening study on the incorporation of different types of luminescent core/shell semiconductor nanocrystals into polymer microparticles (PMPs) by a radical-induced polymerization reaction. Nanocrystals explored include CdSe/CdS QDs of varying CdS shell thickness, a CdSe/ZnS core/shell QD, CdSe/CdS quantum rods (QRs), and CdSe/CdS nanoplatelets (NPLs). Thereby, we focused on the applicability of these NPs for the polymerization synthesis approach used and quantified the preservation of the initial NP luminescence. The spectroscopic characterization of the resulting PMPs revealed the successful staining of the PMPs with luminescent CdSe/CdS QDs and CdSe/CdS NPLs. In contrast, usage of CdSe/CdS QRs and CdSe QDs with a ZnS shell did not yield luminescent PMPs. The results of this study provide new insights into structure–property relationships between NP stained PMPs and the initial luminescent NPs applied for staining and underline the importance of such studies for the performance optimization of NP-stained beads.

Controllable defects in monolayer graphene induced by hydrogen and argon plasma

Graphene has attracted wide attentions since its successfully exfoliation. Honeycomb sp 2 carbon lattice and Dirac semi-metal band structure make graphene a promising material with excellent mechanical strength, thermal conductivity, and carrier mobility. However, the absence of intrinsic bandgap limits its application in semiconductor. Defects in graphene is supposed to modify its band structure and lead to an opened bandgap. Many methods have been demonstrated to introduce defects into graphene, such as chemical reaction, plasma, electron beam, and laser. However, the species of defects are mostly uncontrollable in most treatment processes. In this study, we report three kinds of defects can be controllably induced in graphene via hydrogen (H2) and argon (Ar) plasma. With different parameter and feeding gas, hydrogenated graphene, graphene nanomesh and graphene with vacancies can be well obtained. The defect density can be precisely controlled by tuning plasma power and irradiation time. Morphological, spectroscopic, and electrical characterizations are performed to systematically investigate the defect evolution. Graphene nanomesh and graphene with vacancies show obvious difference for roughness and coverage, whereas the morphology of hydrogenated graphene remains similar with that of as-prepared graphene. For hydrogenated graphene, an opened bandgap of ∼20 meV is detected. For graphene nanomesh and graphene with vacancies, the semiconductive on/off behaviors are observed. We believe this work can provide more details of plasma-induced defects and assist the application of graphene in semiconductor industry.

High Voltage Asymmetric Supercapacitors Using Tungsten‐Doped Mn‐Co Spinel Ferrite Electrodes

AbstractPhysicochemical properties emerging nanomaterials possessing tungsten (W) are unique and the applications could be extended over a wide spectrum as nanocomposite electrodes for effective high voltage energy storage applications. Herewith, W doped spinel ferrite nanostructures was synthesized with facile hydrothermal strategy to get MnCo1.98W0.02O4 (MnCoW). The spectroscopic characterization studies proved spherical subunits embedded onto nanosheets formed by W doped bimetallic oxide with a crystalline phase. The resistance due to charge transfer of the electrodes was reduced which led to enhanced transfer of charge across interface of electrode and electrolyte was addressed upon W doping. Carbon based nanocomposite electrodes endowed by their unique structures and the electrochemical performance with various aqueous electrolytes were tested in an asymmetric supercapacitor application. Excellent capacitance development from 141.2 F g−1 to 203.7 F g−1 was achieved by W doping possessing an energy density of 17.9 Wh kg−1. A superior capacitance retention of 91 % was obtained from MnCoW‐based device right after 10000 cycles (charging/discharging) at 1 A g−1. The designed supercapacitor device employing MnCoW electrode exhibited better lifetime performance during lighting a LED under various angles.

Fast interfacial electrocatalytic desolvation enabling low‐temperature and long‐cycle‐life aqueous Zn batteries

AbstractLow‐temperature zinc batteries (LT‐ZIBs) based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost. However, they suffer from sluggish kinetics with elevated energy barriers due to the dissociation of bulky Zn(H2O)62+ solvation structure and free Zn2+ diffusion, resulting in unsatisfactory lifespan and performance. Herein, dissimilar to solvation shell tuning or layer spacing enlargement engineering, delocalized electrons in cathode through constructing intrinsic defect engineering is proposed to achieve a rapid electrocatalytic desolvation to obtain free Zn2+ for insertion/extraction. As revealed by density functional theory calculations and interfacial spectroscopic characterizations, the intrinsic delocalized electron distribution propels the Zn(H2O)62+ dissociation, forming a reversible interphase and facilitating Zn2+ diffusion across the electrolyte/cathode interface. The as‐fabricated oxygen defect‐rich V2O5 on hierarchical porous carbon (ODVO@HPC) electrode exhibits high capacity robustness from 25 to −20°C. Operating at −20°C, the ODVO@HPC delivers 191 mAh g−1 at 50 A g−1 and lasts for 50 000 cycles at 10 A g−1, significantly enhancing the power density and lifespan under low‐temperature environments in comparison to previous reports. Even with areal mass loading of ~13 mg cm−2, both coin cells and pouch batteries maintain excellent stability and areal capacities, realizing practical high‐performance LT‐ZIBs.

The syntheses of 2-hydroxybenzothiazole substituted cyclotriphosphazenes: Spectroscopic characterizations

The syntheses of 2-hydroxybenzothiazole substituted cyclotriphosphazenes: Spectroscopic characterizations

Self‐Adjustment of Intrinsic Reaction Intermediate on Atomically Dispersed Co2–N6 Binuclear Sites Achieving Boosted Electrocatalytic Oxygen Reduction Performance

AbstractIsolated dual‐atom catalysts (DACs) have sparked enormous research enthusiasm in new energy community due to their great potentials to substitute the state‐of‐the‐art Pt‐based catalysts. Nevertheless, explicitly unraveling the underlying catalytic mechanisms is of critical significance for performance enhancement, yet remains a huge challenge. Herein, the study reports a reliable hard template‐mediated strategy to accomplish the construction of atomically isolated binuclear Co2‐N6 sites stabilized by ultrathin hollow carbon nanospheres (abbreviated as Co2‐DAs@CHNSs). Systematic spectroscopy characterization and theoretic calculations uncover that the Co2‐N6 sites follow a self‐adjusting mechanism caused by the intrinsic OH intermediate. The involvement of the ‐OH energy‐level modifier is found to induce the electron redistribution and alternation of antibonding orbital fillings for the generated Co2‐N6‐OH site, leading to reduced potential‐determining step (PDS) energy barrier, and thus boosted intrinsic activity. Consequently, the well‐managed Co2‐DAs@CHNSs afford outstanding oxygen reduction reaction (ORR) activity with a half‐wave potential of 0.87 V in alkaline electrolyte, overmatching the Pt benchmark. Furthermore, the Co2‐DAs@CHNSs‐assembled aqueous and all‐solid‐state rechargeable zinc–air batteries (ZABs) demonstrate high power density, large specific capacity, and robust stability. The findings offer an innovative avenue to rationally manipulate the electronic structures of active sites for DACs via a powerful self‐ligand modification strategy.

XPS analysis of molecular contamination and sp2 amorphous carbon on oxidized (100) diamond

Abstract The efficacy of oxygen (O) surface terminations on diamond is an important factor for the performance and stability for diamond-based quantum sensors and electronics. Given the wide breadth of O-termination techniques, it can be difficult to discern which method would yield the highest and most consistent O coverage. Furthermore, the interpretation of surface characterization techniques is complicated by surface morphology and purity, which if not accounted for will yield inconsistent determination of the oxygen coverage. We present a comprehensive approach to consistently prepare and analyze oxygen termination of surfaces on (100) single-crystalline diamond. We report on X-ray Photoelectron Spectroscopy (XPS) characterization of diamond surfaces treated with six oxidation methods that include various wet chemical oxidation techniques, photochemical oxidation with UV illumination, and steam oxidation using atomic layer deposition (ALD). Our analysis entails a rigorous XPS peak-fitting procedure for measuring the functionalization of O-terminated diamond. The findings herein have provided molecular-level insights on oxidized surfaces in (100) diamond, including the demonstration of clear correlation between the measured oxygen atomic percentage and the presence of molecular contaminants containing nitrogen, silicon, and sulfur. We also provide a comparison of the sp2 carbon content with the O(1s) atomic percentage and discern a correlation with the diamond samples treated with dry oxidation which eventually tapers off at a max O(1s) atomic percentage value of 7.09 ± 0.40%. Given these results, we conclude that the dry oxidation methods yield some of the highest oxygen amounts, with the ALD water vapor technique proving to be the cleanest technique out of all the oxidation methods explored in this work.

A high internal heat flux and large core in a warm neptune exoplanet.

Interactions between exoplanetary atmospheres and internal properties have long been hypothesized to be drivers of the inflation mechanisms of gaseous planets and apparent atmospheric chemical disequilibrium conditions1. However, transmission spectra of exoplanets has been limited in its ability to observational confirm these theories due to the limited wavelength coverage of HST and inferences of single molecules, mostly H2O (ref. 2). In this work, we present the panchromatic transmission spectrum of the approximately 750 K, low-density, Neptune-sized exoplanet WASP-107b using a combination of HST WFC3, JWST NIRCam and MIRI. From this spectrum, we detect spectroscopic features due to H2O (21σ), CH4 (5σ), CO (7σ), CO2 (29σ), SO2 (9σ), and NH3 (6σ). The presence of these molecules enable constraints on the atmospheric metal enrichment (M/H is 10-18× Solar3), vertical mixing strength (log10Kzz = 8.4-9.0 cm2s-1), and internal temperature (>345 K). The high internal temperature is suggestive of tidally-driven inflation4 acting upon a Neptunelike internal structure, which can naturally explain the planet's large radius and low density. These findings suggest that eccentricity driven tidal heating is a critical process governing atmospheric chemistry and interior structure inferences for a majority of the cool (<1,000K) super-Earth-to-Saturn mass exoplanet population.

Impact of the Surface Microenvironment on the Redox Properties of a Co-Based Molecular Cathode for Selective Aqueous Electrochemical CO2-to-CO Reduction.

Electrode-confined molecular catalysts are promising systems to enable the efficient conversion of CO2 to useful products. Here, we describe the development of an original molecular cathode for CO2 reduction to CO based on the noncovalent integration of a tetraazamacrocyclic Co complex to a carbon nanotube-based matrix. Aqueous electrochemical characterization of the modified electrode allowed for clear observation of a change of redox behavior of the Co center as surface concentration was tuned, highlighting the impact of the catalyst microenvironment on its redox properties. The molecular cathode enabled efficient CO2-to-CO conversion in fully aqueous conditions, giving rise to a turnover number (TONCO) of up to 20 × 103 after 2 h of constant electrolysis at a mild overpotential (η = 450 mV) and with a faradaic efficiency for CO of about 95%. Post operando measurements using electrochemical techniques, inductively coupled plasma, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy characterization of the films demonstrated that the catalysis remained of molecular nature, making this Co-based electrode a new promising alternative for molecular electrocatalytic conversion of CO2-to-CO in fully aqueous media.

Spectroscopy in Characterization of Materials—Developments

The intention of the Special Issue “Advances in Spectroscopy for Materials: Bridging Science and Engineering” is to include various enthusiastic works that focus on the use of various analytical spectroscopic techniques while characterizing materials [...]

Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring.

Aromaticity in organic molecules is well defined, but its role in metal-only rings remains controversial. Here we introduce a supramolecular stabilization approach of a cationic {Bi4} rhomboid within the symmetric charge sphere of two bowl-shaped dianionic calix[4]pyrrolato indinates. Crystallographic and spectroscopic characterization, quantum chemical analysis and magnetically induced ring currents indicate σ-aromaticity in the formally tetracationic 16-valence electron [Bi4]4+ ring. Computational screening for other p-block elements identifies the planar rhomboid as the globally preferred structure for 16-valence electron four-atomic clusters. The aromatic [Bi4]4+ is isoelectronic to the [Al4]4-, a motif previously observed as antiaromatic in Li3[Al4]- in the gas phase. Thus, subtle factors such as charge isotropy seem to decide over aromaticity or antiaromaticity, advising for caution in debates based on the Hückel model-a concept valid for second-row elements but less deterministic for the heavier congeners.

Photocatalytic activity and electrochemical properties of a ternary-based-TiO2 nanocomposite

A TiO2 photocatalyst modified with g-C3N4 and different wt% of CuO, is performed via hydrothermal method. The structural, morphological and spectroscopic characterizations are carried out. The ternary composite, g-C3N4/CuO/TiO2, exhibits greater photocatalytic activity than CuO/TiO2. The highest degradation of Levofloxacin reaches 99% and 44%, after 10 and 60 min UV irradiation over ternary and binary composites for 20 wt% of CuO, respectively, with a concentration of 5.10−3 g/L of LEVO and a photocatalyst mass of 2.10−2 g. The stability of g-C3N4/CuO/TiO2 is confirmed allowing its reuse for five successive cycles with a longer treatment time. Under solar irradiation, the degradation yield of Levo using g-C3N4/CuO/TiO2 is 100% after only 20 min. The as-synthesized nanocomposite present interesting electrochemical properties. In the medium-frequency region, the diameter of the semicircle for the g-C3N4/CuO/TiO2 electrode is much smaller than that of the CuO/TiO2 electrode, indicating a lower charge-transfer resistance.

Compositional alteration of low dimensional nickel sulfides under hydrogen evolution reaction conditions in alkaline media

Developing cost-effective electrodes for electrochemical water splitting with minimal kinetic losses remains a primary challenge in water electrolysis. Nickel-based dichalcogenides, particularly sulfides, have emerged as promising candidates for the hydrogen evolution reaction (HER). However, the stability of various nickel sulfide (NixSy) phases under cathodic potentials in alkaline electrolytes is subject to debate. In this study, we investigate the HER activity and durability of both 2-dimensional (2D) and 3-dimensional (3D) NixSy nanostructures with diverse chemical compositions. Through cross-correlation analysis of spectroscopic and electrochemical characterization data, we elucidate the transformation behavior of these materials under operating conditions. Our findings reveal that NiS2 tends to undergo conversion to nickel hydroxide (Ni(OH)2), while Ni-rich phases like Ni3S4 and NiS exhibit greater stability. Furthermore, we demonstrate that in 3D nanostructures, the initial formation of a protective hydroxide layer on the surface inhibits further sulfide transformation. This nickel sulfide/hydroxide composite shows an improved HER activity with lower onset potential (−0.25 V), Tafel slope (105 mV s−1), and charge transfer resistance (17.3 Ω).

Copper-doped titanium dioxide nanoparticles decorated on 2D-hexagonal boron nitride nanosheets for susceptible electrochemical detection of an anti-cancer drug in environmental and biological samples.

Chlorambucil (CML) cures chronic lymphatic leukemia (white blood cell cancer). A high dose of CML can cause several side effects like bone marrow suppression, anemia, peripheral neuropathy, and infertility in the human body. In this research, we have synthesized a nanocomposite based on copper-doped titanium dioxide (CuTiO2) adorned with 2D hexagonal boron nitride (CuTiO2@BN) for the efficient electrochemical detection of CML. A series of characterization techniques FT-IR, XRD, Raman spectroscopy, SEM, TEM, EDAX XPS, and electrochemical characterization were used to analyze the CuTiO2@BN nanocomposite structural and morphological compositions. The sensing performance of the CuTiO2@BN modified GCE for CML detection has been assessed using voltammetry methods. The chronoamperometry technique analyzed the kinetics of the electrochemical oxidation of CML at CuTiO2@BN/GCE. The CuTiO2@BN-based glassy carbon electrode (GCE) has a synergetic electro-catalytic effect on CML oxidation due to its many active sites, enhanced surface area, fast charge transfer, and numerous defects. For the detection of CML, the suggested electrochemical sensor exhibits excellent selectivity, low limit of detection (LOD) as found 5.0nM, wide linear ranges (0.02-8000µM), and quick reaction times.

Spectroscopic Characterization of Biomaterials for Tissue Engineering Applications

Spectroscopic Characterization of Biomaterials for Tissue Engineering Applications

Extension of nature's NIR-I chromophore into the NIR-II region.

The development of chromophores that absorb in the near-infrared (NIR) region beyond 1000 nm underpins numerous applications in medical and energy sciences, yet also presents substantial challenges to molecular design and chemical synthesis. Here, the core bacteriochlorin chromophore of nature's NIR absorbers, bacteriochlorophylls, has been adapted and tailored by annulation in an effort to achieve absorption in the NIR-II region. The resulting bacteriochlorin, Phen2,1-BC, contains two annulated naphthalene groups spanning meso,β-positions of the bacteriochlorin and the 1,2-positions of the naphthalene. Phen2,1-BC was prepared via a new synthetic route. Phen2,1-BC is an isomer of previously examined Phen-BC, which differs only in attachment via the 1,8-positions of the naphthalene. Despite identical π-systems, the two bacteriochlorins have distinct spectroscopic and photophysical features. Phen-BC has long-wavelength absorption maximum (912 nm), oscillator strength (1.0), and S1 excited-state lifetime (150 ps) much different than Phen2,1-BC (1292 nm, 0.23, and 0.4 ps, respectively). These two molecules and an analogue with intermediate characteristics bearing annulated phenyl rings have unexpected properties relative to those of non-annulated counterparts. Understanding the distinctions requires extending concepts beyond the four-orbital-model description of tetrapyrrole spectroscopic features. In particular, a reduction in symmetry resulting from annulation results in electronic mixing of x- and y-polarized transitions/states, as well as vibronic coupling that together reduce oscillator strength of the long-wavelength absorption manifold and shorten the S1 excited-state lifetime. Collectively, the results suggest a heuristic for the molecular design of tetrapyrrole chromophores for deep penetration into the relatively unutilized NIR-II region.

Lone-Pair-p Bond Strength Unveiled by a Combined Experimental and Computational Study.

A series of naphthalene-diimide (NDI) and perylene-diimide (PDI) connected bis-N-heterocyclic carbene complexes of iridium (III) have been prepared and fully characterized. The analysis of their NMR spectroscopic features, together their molecular structures show that these species display lone pair-p interactions between the chloride ligands of the Ir(III) complex and the heterocycles of the NDI/PDI moieties. The detection of this type of interaction in solution is due to the formation of two atropisomers, which are formed as a result of the restricted rotation about the Ir-Ccarbene bond imposed by the (Cl)lp…p interaction. Variable temperature 1H NMR analysis allowed to determine the strength of this non-covalent interaction, which lies between DH = 6.6-10 kcal/mol. The computational studies performed fully support the experimental findings. Our study demonstrates that this type of lp…p interaction is comparable to strong hydrogen bonding.