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A wide range of artificially twist‐stacked van der Waals materials offer versatile building blocks for quantum optoelectronic devices. Among these, twisted bilayer MoTe2 has excellent optical properties in the near‐infrared range and can be integrated with silicon photonics. While recent studies mainly focus on the emission properties in twisted bilayer MoTe2, a comprehensive investigation of how Moiré superlattice affects phonon modes in twisted thin‐layer MoTe2 remains unexplored. These phonon modes can serve as indicators of stacking configuration and interface uniformity. Here, a series of twisted bilayer and tetralayer MoTe2 with precisely controlled twist angles ranging from 0° to 60° are prepared. Using polarization‐dependent low‐frequency Raman spectroscopy, the evolution of interlayer phonon modes at different twist angles is identified. Additionally, a range of acoustic phonon modes activated by Moiré potentials in both twisted bilayer MoTe2 and twisted tetralayer MoTe2 are observed and analyzed. The findings provide experimental evidence of the interlayer phonon coupling and Moiré phonons in MoTe2, offering insights for the future development of near‐infrared optoelectronic devices based on twisted thin‐layer MoTe2. [ABSTRACT FROM AUTHOR]

A wide range of artificially twist‐stacked van der Waals materials offer versatile building blocks for quantum optoelectronic devices. Among these, twisted bilayer MoTe2 has excellent optical properties in the near‐infrared range and can be integrated with silicon photonics. While recent studies mainly focus on the emission properties in twisted bilayer MoTe2, a comprehensive investigation of how Moiré superlattice affects phonon modes in twisted thin‐layer MoTe2 remains unexplored. These phonon modes can serve as indicators of stacking configuration and interface uniformity. Here, a series of twisted bilayer and tetralayer MoTe2 with precisely controlled twist angles ranging from 0° to 60° are prepared. Using polarization‐dependent low‐frequency Raman spectroscopy, the evolution of interlayer phonon modes at different twist angles is identified. Additionally, a range of acoustic phonon modes activated by Moiré potentials in both twisted bilayer MoTe2 and twisted tetralayer MoTe2 are observed and analyzed. The findings provide experimental evidence of the interlayer phonon coupling and Moiré phonons in MoTe2, offering insights for the future development of near‐infrared optoelectronic devices based on twisted thin‐layer MoTe2. [ABSTRACT FROM AUTHOR]

Attenuated total reflection infrared (ATR-IR, 4000–400 cm–1), ATR-far-IR (ATR-FIR, 400–50 cm–1), and Raman spectra (4000–10 cm–1) were measured for calcium carbonate, three kinds of minerals (calcite, aragonite, and quartz), two kinds of rocks (obsidian and pumice), and four kinds of biogenic minerals, i.e., coral (aragonite), Ruditapes philippinarum (aragonite), Meretrix lusoria (aragonite), and Corbicula japonica (aragonite), to investigate the polymorphism of minerals and biogenic minerals, differences in the crystal structure among aragonite and aragonite biogenic minerals, water in the minerals and biogenic minerals, Boson peaks of obsidian and pumice, very small amounts of carotenoids in the three kinds of shells, and so on. In this study, we put some emphasis on the low-frequency region of IR (FIR) and Raman spectra. ATR-FIR spectra were measured down to 50 cm–1 and Raman spectra were obtained down to 10 cm–1. Second derivative spectra were calculated for the FIR spectra. It has been found from the present study that the FIR spectra are the most powerful for exploring polymorphism and differences in the crystal structure among aragonite and aragonite biogenic minerals. A Boson peak, which is a characteristic low-frequency Raman band for amorphous materials, was observed at around 40 cm–1 in the Raman spectra of obsidian and pumice. The Boson peak of pumice is located at a lower frequency by 12 cm–1 than that of obsidian, indicating that the mean atomic volume of pumice is larger than that of obsidian. The present study has revealed that IR spectra are useful to investigate the amounts and structure of fluid and bound water. Moreover, it has also been found that Raman spectra can detect a very tiny amount of carotenoids in the shells due to the resonance Raman effect. Graphical abstract This is a visual representation of the abstract. [ABSTRACT FROM AUTHOR]

The antiferromagnetic (AFM) spin waves are promising for being utilized in highspeed and energy-efficient information processing. However, the excitation and detection of terahertz spin waves in AFM systems is challenging. Here, we demonstrate low-frequency Raman spectroscopy as a powerful tool for spin-wave detection in AFM systems. We present a systematic study of AFM magnons in Cr2O3, a prototypical uniaxial antiferromagnet, via Raman measurements down to 2.3 cm-1 (69 GHz). We resolved the magnon Zeeman splitting and the spin-flop transition. We further determined the sign of angular momentum of the magnon branches via polarization-resolved Raman processes. We also obtained the anisotropy energy, the g-factor, and the spin-flop field of Cr2O3 as a function of temperatures and magnetic fields. A spin-wave renormalization theory accounts for all experimental observations. [ABSTRACT FROM AUTHOR]

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The investigation of twisted stacked few‐layer MoS2 has revealed novel electronic, optical, and vibrational properties over an extended period. For the successful integration of twisted stacked few‐layer MoS2 into a wide range of applications, it is crucial to employ a noninvasive, versatile technique for characterizing the layered architecture of these complex structures. In this work, we introduce a machine learning‐assisted low‐frequency Raman spectroscopy method to characterize the twist angle of few‐layer stacked MoS2 samples. A feedforward neural network (FNN) is utilized to analyze the low‐frequency breathing mode as a function of the twist angle. Moreover, using finite difference method (FDM) and density functional theory (DFT) calculations, we show that the low‐frequency Raman spectra of MoS2 are mainly influenced by the effect of the nearest and second nearest layers. A new improved linear chain model (TA‐LCM) with taking the twist angle into the consideration is developed to understand the interlayer breathing modes of stacked few‐layer MoS2. This approach can be extended to other 2D materials systems and provides an intelligent way to investigate naturally stacked and twisted interlayer interactions. [ABSTRACT FROM AUTHOR]

Low-frequency Raman spectroscopy (LFRS) is a valuable tool to detect the solid state of amorphous and crystalline drugs in solid dosage forms and the transformation of drugs between different polymorphic forms. It has also been applied to track the solubilisation of solid drugs as suspensions in milk and infant formula during in vitro digestion. This study reports the use of LFRS as an approach to probe drug precipitation from a lipid-based drug delivery system (medium-chain self-nanoemulsifying drug delivery system, MC-SNEDDS) during in vitro digestion. Upon lipolysis of the digestible components in MC-SNEDDS containing fenofibrate as a model drug, sharp phonon peaks appeared at the low-frequency Raman spectral region (<200 cm−1), indicating the precipitation of fenofibrate in a crystalline form from the formulation. Two multivariate data analysis approaches (principal component analysis and partial least squares discriminant analysis) and one univariate analysis approach (band ratios) were explored to track these spectral changes over time. The low-frequency Raman data produces results in good agreement with in situ small angle X-ray scattering (SAXS) measurements with all data analysis approaches used, whereas the mid-frequency Raman requires the use of PLS-DA to gain similar results. This suggests that LFRS can be used as a complementary, and potentially more accessible, technique to SAXS to determine the kinetics of drug precipitation from lipid-based formulations. [ABSTRACT FROM AUTHOR]

The use of low-frequency Raman spectroscopy (LFRS; ω < 150 cm−1) is booming in the pharmaceutical industry. Specific processing of spectra is required to use the wealth of information contained in this spectral region. Spectra processing and the use of LFRS for analyzing phase transformations in molecular materials are detailed herein from investigations on the devitrification of ibuprofen. LFRS was used to analyze the dehydration mechanism of two hydrates (theophylline and caffeine) of the xanthine family. Two mechanisms of solid-state transformation in theophylline were determined depending on the relative humidity (RH) and temperature. At room temperature and 1% RH, dehydration is driven by the diffusion mechanism, while under high RH (>30%), kinetic laws are typical of nucleation and growth mechanism. By increasing the RH, various metastability driven crystalline forms were obtained mimicking successive intermediate states between hydrate form and anhydrous form achieved under high RH. In contrast, the dehydration kinetics of caffeine hydrate under various RH levels can be described by only one master curve corresponding to a nucleation mechanism. Various metastability driven states were achieved depending on the RH, which can be described as intermediate between forms I and II of anhydrous caffeine. [ABSTRACT FROM AUTHOR]

Transdermal administration can be considered as an interesting route to overcome the side-effects inherent to oral intake. Designing topical formulations with maximum drug efficiency requires the optimization of the permeation and the stability of the drug. The present study focuses on the physical stability of amorphous drugs within the formulation. Ibuprofen is commonly used in topical formulations and then was selected as a model drug. Additionally, its low Tg allows easy, unexpected recrystallization at room temperature with negative consequence on skin penetration. In this study, the physical stability of amorphous ibuprofen was investigated in two types of formulations: (i) in terpenes-based deep eutectic solvents (DES) and (ii) in arginine-based co-amorphous blends. The phase diagram of ibuprofen:L-menthol was mainly analyzed by low-frequency Raman spectroscopy, leading to the evidence of ibuprofen recrystallization in a wide range of ibuprofen concentration. By contrast, it was shown that amorphous ibuprofen is stabilized when dissolved in thymol:menthol DES. Forming co-amorphous arginine–ibuprofen blends by melting is another route for stabilizing amorphous ibuprofen, while recrystallization was detected in the same co-amorphous mixtures obtained by cryo-milling. The mechanism of stabilization is discussed from determining Tg and analyzing H-bonding interactions by Raman investigations in the C=O and O–H stretching regions. It was found that recrystallization of ibuprofen was inhibited by the inability to form dimers inherent to the preferential formation of heteromolecular H-bonding, regardless of the glass transition temperatures of the various mixtures. This result should be important for predicting ibuprofen stability within other types of topical formulations. [ABSTRACT FROM AUTHOR]

The solid-state landscape of carbamazepine during its dehydration was explored using Raman spectroscopy in the low- (−300 to −15, 15 to 300) and mid- (300 to 1800 cm−1) frequency spectral regions. Carbamazepine dihydrate and forms I, III, and IV were also characterized using density functional theory with periodic boundary conditions and showed good agreement with experimental Raman spectra with mean average deviations less than 10 cm−1. The dehydration of carbamazepine dihydrate was examined under different temperatures (40, 45, 50, 55, and 60 °C). Principal component analysis and multivariate curve resolution were used to explore the transformation pathways of different solid-state forms during the dehydration of carbamazepine dihydrate. The low-frequency Raman domain was able to detect the rapid growth and subsequent decline of carbamazepine form IV, which was not as effectively observed by mid-frequency Raman spectroscopy. These results showcased the potential benefits of low-frequency Raman spectroscopy for pharmaceutical process monitoring and control. [ABSTRACT FROM AUTHOR]

Mesoporous silica (MPS) carriers are considered as a promising strategy to increase the solubility of poorly soluble drugs and to stabilize the amorphous drug delivery system. The development by the authors of a solvent-free method (milling-assisted loading, MAL) made it possible to manipulate the physical state of the drug within the pores. The present study focuses on the effects of the milling intensity and the pore architecture (chemical surface) on the physical state of the confined drug and its release profile. Ibuprofen (IBP) and SBA-15 were used as the model drug and the MPS carrier, respectively. It was found that decreasing the milling intensity promotes nanocrystallization of confined IBP. Scanning electron microscopy and low-frequency Raman spectroscopy investigations converged into a bimodal description of the size distribution of particles, by decreasing the milling intensity. The chemical modification of the pore surface with 3-aminopropyltriethoxisylane also significantly promoted nanocrystallization, regardless of the milling intensity. Combined analyses of drug release profiles obtained on composites prepared from unmodified and modified SBA-15 with various milling intensities showed that the particle size of composites has the greatest influence on the drug release profile. Tuning drug concentration, milling intensity, and chemical surface make it possible to easily customize drug delivery. [ABSTRACT FROM AUTHOR]

Artemisinin (ART) is a most promising antimalarial agent. However, its low aqueous solubility limits its oral absorption, resulting in low bioavailability. In this study, we have successfully discovered a novel cocrystal with 2-methyl resorcinol (ART-2MRE) providing improved solubility compared with a previously reported cocrystal with resorcinol (ART-RES). Single crystal X-ray structure analysis revealed that the ART-2MRE cocrystal was composed of ART and 2MRE in a molar ratio of 2 : 1. Though the ART-2MRE and ART-RES cocrystals were found to have similarities in their crystal structures, with one layer of a cocrystal former and two layers of ART arranged in alternating rows, the ART-2MRE cocrystal showed higher dissolution rate than ART-RES cocrystal. In situ real-time low-frequency (LF) Raman monitoring and powder X-ray diffraction (PXRD) measurements of the crystals during the dissolution test proved useful to investigate the dissolution behavior of the cocrystals. Low-frequency Raman monitoring revealed that as dissolution progressed, there was a continuous shift from the peak unique to the ART-2MRE cocrystal to the peak unique to the ART stable form. Similar observations were obtained in PXRD measurements as well. Furthermore, experiments were conducted by adding a polymer to the dissolution test solution to investigate the dissolution behavior under supersaturation, indicating the possibility of differences in the dissolution behavior between the ART-2MRE cocrystal and ART-RES cocrystal. Understanding the dissolution behavior from cocrystals is essential in developing cocrystals. [ABSTRACT FROM AUTHOR]

The development of non-contact in situ techniques for monitoring cure kinetics has the potential to greatly improve both resin formulation and processing. We have recently shown that low-frequency Raman spectroscopy is a viable method for assessing resin structural cure kinetics and complements the traditional chemical conversion determined from the fingerprint region of the spectrum. In this work, we further evaluate the relationship between structural and chemical conversion by investigating two chemically identical yet rheologically different interpenetrating polymer network resin formulations. Rheological analysis demonstrates a relationship between structural conversion and storage modulus, which is not observed in the chemical conversion data. We show that one can produce master cure kinetics curves with comparable kinetic constants using both the chemical and structural conversion methodologies. Parametric analysis of the structural conversion, chemical conversion, and photorheological conversion was combined with a semi-empirical model for the storage shear modulus as a function of the extent of cure. [ABSTRACT FROM AUTHOR]

The use of low-frequency Raman spectroscopy (LFRS; ω < 150 cm−1) is booming in the pharmaceutical industry. Specific processing of spectra is required to use the wealth of information contained in this spectral region. Spectra processing and the use of LFRS for analyzing phase transformations in molecular materials are detailed herein from investigations on the devitrification of ibuprofen. LFRS was used to analyze the dehydration mechanism of two hydrates (theophylline and caffeine) of the xanthine family. Two mechanisms of solid-state transformation in theophylline were determined depending on the relative humidity (RH) and temperature. At room temperature and 1% RH, dehydration is driven by the diffusion mechanism, while under high RH (>30%), kinetic laws are typical of nucleation and growth mechanism. By increasing the RH, various metastability driven crystalline forms were obtained mimicking successive intermediate states between hydrate form and anhydrous form achieved under high RH. In contrast, the dehydration kinetics of caffeine hydrate under various RH levels can be described by only one master curve corresponding to a nucleation mechanism. Various metastability driven states were achieved depending on the RH, which can be described as intermediate between forms I and II of anhydrous caffeine.

Low-frequency Raman spectroscopy (LFRS) is a valuable tool to detect the solid state of amorphous and crystalline drugs in solid dosage forms and the transformation of drugs between different polymorphic forms. It has also been applied to track the solubilisation of solid drugs as suspensions in milk and infant formula during in vitro digestion. This study reports the use of LFRS as an approach to probe drug precipitation from a lipid-based drug delivery system (medium-chain self-nanoemulsifying drug delivery system, MC-SNEDDS) during in vitro digestion. Upon lipolysis of the digestible components in MC-SNEDDS containing fenofibrate as a model drug, sharp phonon peaks appeared at the low-frequency Raman spectral region (−1), indicating the precipitation of fenofibrate in a crystalline form from the formulation. Two multivariate data analysis approaches (principal component analysis and partial least squares discriminant analysis) and one univariate analysis approach (band ratios) were explored to track these spectral changes over time. The low-frequency Raman data produces results in good agreement with in situ small angle X-ray scattering (SAXS) measurements with all data analysis approaches used, whereas the mid-frequency Raman requires the use of PLS-DA to gain similar results. This suggests that LFRS can be used as a complementary, and potentially more accessible, technique to SAXS to determine the kinetics of drug precipitation from lipid-based formulations.

Transdermal administration can be considered as an interesting route to overcome the side-effects inherent to oral intake. Designing topical formulations with maximum drug efficiency requires the optimization of the permeation and the stability of the drug. The present study focuses on the physical stability of amorphous drugs within the formulation. Ibuprofen is commonly used in topical formulations and then was selected as a model drug. Additionally, its low Tg allows easy, unexpected recrystallization at room temperature with negative consequence on skin penetration. In this study, the physical stability of amorphous ibuprofen was investigated in two types of formulations: (i) in terpenes-based deep eutectic solvents (DES) and (ii) in arginine-based co-amorphous blends. The phase diagram of ibuprofen:L-menthol was mainly analyzed by low-frequency Raman spectroscopy, leading to the evidence of ibuprofen recrystallization in a wide range of ibuprofen concentration. By contrast, it was shown that amorphous ibuprofen is stabilized when dissolved in thymol:menthol DES. Forming co-amorphous arginine–ibuprofen blends by melting is another route for stabilizing amorphous ibuprofen, while recrystallization was detected in the same co-amorphous mixtures obtained by cryo-milling. The mechanism of stabilization is discussed from determining Tg and analyzing H-bonding interactions by Raman investigations in the C=O and O–H stretching regions. It was found that recrystallization of ibuprofen was inhibited by the inability to form dimers inherent to the preferential formation of heteromolecular H-bonding, regardless of the glass transition temperatures of the various mixtures. This result should be important for predicting ibuprofen stability within other types of topical formulations.

The solid-state landscape of carbamazepine during its dehydration was explored using Raman spectroscopy in the low- (−300 to −15, 15 to 300) and mid- (300 to 1800 cm−1) frequency spectral regions. Carbamazepine dihydrate and forms I, III, and IV were also characterized using density functional theory with periodic boundary conditions and showed good agreement with experimental Raman spectra with mean average deviations less than 10 cm−1. The dehydration of carbamazepine dihydrate was examined under different temperatures (40, 45, 50, 55, and 60 °C). Principal component analysis and multivariate curve resolution were used to explore the transformation pathways of different solid-state forms during the dehydration of carbamazepine dihydrate. The low-frequency Raman domain was able to detect the rapid growth and subsequent decline of carbamazepine form IV, which was not as effectively observed by mid-frequency Raman spectroscopy. These results showcased the potential benefits of low-frequency Raman spectroscopy for pharmaceutical process monitoring and control.

Sb2Se3 has emerged as an important photoelectrochemical (PEC) and photovoltaic (PV) material due to its rapid rise in photoconversion efficiencies. However, Sb2Se3 has a complex defect chemistry, which reduces the maximum photovoltage. Thus, it is important to understand these defects and develop defect passivation strategies in Sb2Se3. A comprehensive investigation of the charge carrier dynamics of Sb2Se3 and the influence of sulfur treatment on its optoelectronic properties is performed using time‐resolved microwave conductivity (TRMC), photoluminescence (PL) spectroscopy, and low‐frequency Raman spectroscopy (LFR). The key finding in this work is that upon sulfur treatment of Sb2Se3, the carrier lifetime is increased by the passivation of deep defects in Sb2Se3 in both the surface region and the bulk, which is evidenced by increased charge carrier lifetime of TRMC decay dynamics, increased radiative recombination efficiency, decreased deep defect level emission (PL), and the emergence of new vibration modes by LFR. [ABSTRACT FROM AUTHOR]

The organic glass-forming dibutyl phthalate (DBP) has been studied applying low-frequency Raman and Brillouin spectroscopy in the temperature range from 90 K to 200 K, covering glassy and liquid states. Spectra of fast relaxation in the GHz-THz frequency range were determined from the inelastic light scattering spectra. The line width and position of the Brillouin peak were used to determine the Q-1 -factor, which is inversely proportional to susceptibility at the Brillouin peak frequency. It was discovered that the temperature evolution of the fast relaxation susceptibility and the Q-1 -factor agree well with a mobility parameter from pulse EPR experiment. The findings show that peculiarities in the temperature dependence the EPR data found early for DBP have are accompanied by a redistribution of the relaxation times. [ABSTRACT FROM AUTHOR]

Substrates provide the necessary support for scientific explorations of numerous promising features and exciting potential applications in two-dimensional (2D) transition metal dichalcogenides (TMDs). To utilize substrate engineering to alter the properties of 2D TMDs and avoid introducing unwanted adverse effects, various experimental techniques, such as high-frequency Raman spectroscopy, have been used to understand the interactions between 2D TMDs and substrates. However, sample-substrate interaction in 2D TMDs is not yet fully understood due to the lack of systematic studies by techniques that are sensitive to 2D TMD-substrate interaction. This work systematically investigates the interaction between tungsten disulfide (WS2) monolayers and substrates by low-frequency Raman spectroscopy, which is very sensitive to WS2-substrate interaction. Strong coupling with substrates is clearly revealed in chemical vapor deposition (CVD)-grown monolayer WS2 by its low-wavenumber interface mode. It is demonstrated that the enhanced sample-substrate interaction leads to tensile strain on monolayer WS2, which is induced during the cooling process of CVD growth and could be released for monolayer WS2 sample after transfer or fabricated by an annealing-free method such as mechanical exfoliation. These results not only suggest the effectiveness of low-frequency Raman spectroscopy for probing sample-substrate interactions in 2D TMDs, but also provide guidance for the design of high-performance devices with the desired sample-substrate coupling strength based on 2D TMDs. [ABSTRACT FROM AUTHOR]

Mesoporous silica (MPS) carriers are considered as a promising strategy to increase the solubility of poorly soluble drugs and to stabilize the amorphous drug delivery system. The development by the authors of a solvent-free method (milling-assisted loading, MAL) made it possible to manipulate the physical state of the drug within the pores. The present study focuses on the effects of the milling intensity and the pore architecture (chemical surface) on the physical state of the confined drug and its release profile. Ibuprofen (IBP) and SBA-15 were used as the model drug and the MPS carrier, respectively. It was found that decreasing the milling intensity promotes nanocrystallization of confined IBP. Scanning electron microscopy and low-frequency Raman spectroscopy investigations converged into a bimodal description of the size distribution of particles, by decreasing the milling intensity. The chemical modification of the pore surface with 3-aminopropyltriethoxisylane also significantly promoted nanocrystallization, regardless of the milling intensity. Combined analyses of drug release profiles obtained on composites prepared from unmodified and modified SBA-15 with various milling intensities showed that the particle size of composites has the greatest influence on the drug release profile. Tuning drug concentration, milling intensity, and chemical surface make it possible to easily customize drug delivery.

The sub-200 cm−1 (sub-6 THz) vibrations of molecular crystals provide identifying features that are characteristic of each solid sample under study. These distinctive vibrational spectra have driven the development of new techniques and instrumentation in analytical spectroscopy. As terahertz time-domain spectroscopy and low-frequency Raman spectroscopy become increasingly prevalent in non-specialist laboratories, the need for a common set of spectral standards for use across these techniques becomes imperative. To meet this need, α-lactose monohydrate, biotin, and L-cystine are proposed here as molecular standards to evaluate instrument performance with both terahertz and Raman spectroscopies, as well serve as benchmarks for quantum mechanical simulations and analyses of these spectra. These substances all reveal a series of readily discernable peaks across the low-frequency region and also over a range of temperatures (295–50 K) making them even more useful. The often overlooked aspect of detailed spectral interpretation and assignment is directly addressed with rigorous solid-state density functional theory simulations of the three compounds based on a standard computational framework. By investigating these proposed molecular crystal standards with commonly available experimental and theoretical approaches, a set of realistic performance expectations can be achieved for both commercial instrumentation and software being used in low-frequency vibrational spectroscopy. [ABSTRACT FROM AUTHOR]

Two new peroxosolvates of drug-like compounds were synthesized and studied by a combination of X-ray crystallographic, Raman spectroscopic methods, and periodic DFT computations. The enthalpies of H-bonds formed by hydrogen peroxide (H2O2) as a donor and an acceptor of protons were compared with the enthalpies of analogous H-bonds formed by water (H2O) in isomorphic (isostructural) hydrates. The enthalpies of H-bonds formed by H2O2 as a proton donor turned out to be higher than the values of the corresponding H-bonds formed by H2O. In the case of H2O2 as a proton acceptor in H-bonds, the ratio appeared reversed. The neutral O∙∙∙H-O/O∙∙∙H-N bonds formed by the lone electron pair of the oxygen atom of water were the strongest H-bonds in the considered crystals. In the paper, it was found out that the low-frequency Raman spectra of isomorphous crystalline hydrate and peroxosolvate of N-(5-Nitro-2-furfurylidene)-1-aminohydantoin are similar. As for the isostructural hydrate and peroxosolvate of the salt of protonated 2-amino-nicotinic acid and maleic acid monoanion, the Raman spectra are different.

A new method for determining solubility lines of drugs in polymers, based on low-frequency Raman spectroscopy measurements, is described and the results obtained by this method are compared with those obtained using a more classical method based on differential scanning calorimetry investigations. This method was applied to the paracetamol/PVP system using molecular and crystalline dispersions (MCD) rather than usual physical mixtures to reach faster the equilibrium saturated states and make the determination of the solubility line more rapid. [ABSTRACT FROM AUTHOR]

Abstract Mesoporous silica carriers have recently gained interest in the pharmaceutical domain because of their potential to significantly increase the solubility of poorly water-soluble drugs, by adsorbing the active molecule in an amorphous and relatively stable state. However, the use of organic solvents for drug loading and the limited loading capacity are real drawbacks in the context of therapeutic use. The present work shows that co-milling of porous SBA-15 matrix with the drug makes it possible the drug loading without significant damage for the structure of the matrix, enhancing thereby the capacity of loading to almost 40 wt%. Combining calorimetric, thermogravimetric, and low-frequency Raman investigations has allowed us to determine optimum conditions of loading, and to analyze the physical state, the molecular mobility and the phase transformations of the confined drug upon heating. It was shown that the physical state of ibuprofen (IBP) confined to silica carriers was amorphous between temperatures T g and T m of the bulk form of IBP. Graphical abstract Image 1 Highlights • Ibuprofen was loaded within SBA-15 by co-milling at room temperature. • Crystal - amorphous solid-state conversion is driven by confinement in 6.5 nm pores. • The loading capacity of API is about wt 40%. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Cocrystallization is an attractive and promising technology that can improve the physical properties of formulations of active pharmaceutical ingredients (APIs). We have developed a "nano-spot method" that can evaluate the crystalline form on the nanogram scale. In this study, the following studies were performed to obtain versatile and comprehensive improvements to the nano-spot method: modification of the sample solution, application of solvent vapor exposure to attempt the precipitation of various states of crystals, and adoption of low-frequency Raman spectroscopy. Carbamazepine was used as a model API and cocrystallization screening was examined with 12 cocrystal formers (coformers). In the case of combinations that are already known to form cocrystals, spectra similar to those of previously reported cocrystals or new spectra were obtained. It was considered that the reported cocrystals or new polymorphs were obtained. In contrast, in the case of the combination which has been reported not to form a cocrystal, the spectra were consistent with that for the physical mixture of API and coformer, suggesting that a cocrystal also did not form in this screening. In addition, the newly adopted low-frequency Raman spectroscopy enabled the high-sensitive detection of the crystalline form. [ABSTRACT FROM AUTHOR]

Adsorption of gut relevant biomolecules onto particles after oral administration of solid oral dosage forms is expected to form a "gastrointestinal corona", which could influence solution-mediated solid-state transformations on exposure of drug particles to gastrointestinal fluids. Low-frequency Raman (LFR) spectroscopy was used in this study to investigate in situ solid-state phase transformations under biorelevant temperature and pH conditions along with the presence of biomolecules. Melt-quenched amorphous indomethacin was used as a model solid particulate, and its solid-state behavior was evaluated at 37 °C and pH 1.2-6.8 with or without the presence of typical bile salt/phospholipid mixtures emulating fed-state conditions. Overall, a change in the solid-state transformation pathway from amorphous to crystalline drug was observed, where an intermediate ε-form that initially formed at pH 6.8 was suppressed by the addition of endogenous gastrointestinal biomolecules. These solid-state changes were corroborated using time-resolved synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS). Additionally, the bile salt and phospholipid mixture partly prevented the otherwise strong aggregation between drug particles at more acidic conditions (pH ≤ 4.5) and helped to shift the balance against the intrinsic hydrophobicity of indomethacin as well as the plasticization effect brought about by the physiological temperature (i.e., the stickiness arising from the supercooled liquid state at 37 °C). The overall results highlight the importance of evaluating the impact that endogenous biomolecules may have on the solid-state characteristics of drug molecules in dissolution media, where analytical tools such as LFR spectroscopy can serve as an attractive avenue for accessing time-resolved solid-state information on time-scales that are difficult to achieve with other techniques such as X-ray diffraction.

Differential scanning calorimetry, X-ray diffraction analysis, transmission electron microscopy, high- and low-frequency Raman and optical spectroscopy were applied to the study of structural transformations in glass of the K 2 O – ZnO – Al 2 O 3 – SiO 2 system codoped with Er 2 O 3 and Yb 2 O 3 and subjected to heat-treatments at 680–1300 °C. Transparent glass-ceramics based on ZnO nanocrystals are prepared by heat-treatments at 680–800 °C, while at 860–900 °C, β-Zn 2 SiO 4 (β-willemite) nanocrystals precipitate in addition to ZnO; α-Zn 2 SiO 4 nanocrystals appear additionally at 950 °C, and the material loses transparency. Opaque glass-ceramic prepared by heat-treatments at 1000 °C contains only crystals of ZnO and α-Zn 2 SiO 4 , while crystallization of potassium aluminosilicates, KAlSi 2 O 6 (from the surface) and KAlSiO 4 (from the bulk) in addition to ZnO and α-Zn 2 SiO 4 , is observed at above 1000 °C. Optical absorption and luminescence of the initial glass and GCs are reported. A shift of the UV absorption edge and the near-IR losses due to the free charge carrier scattering are indications of the ZnO crystallization. Multiple visible emissions from the glass and GCs are determined by the Er 3+ ions, nanocrystals of α-Zn 2 SiO 4 and defects of the ZnO nanocrystals. The color of the latter emission can be tuned by varying the heat-treatment temperature. The rare-earth ions (RE 3+ ) do not enter into the Zn-containing nanocrystals and remain in the residual glassy phase until ~ 1200 °C, when the RE silicates (RE 2 Si 2 O 7 ) are formed resulting in structured intense Er 3+ emission. [ABSTRACT FROM AUTHOR]

In recent years, to guarantee a quality-by-design approach to the development of pharmaceutical products, it is important to identify properties of raw materials and excipients in order to determine critical process parameters and critical quality attributes. Feedback obtained from real-time analyses using various process analytical technology (PAT) tools has been actively investigated. In this study, in situ monitoring using low-frequency (LF) Raman spectroscopy (10–200 cm −1 ), which may have higher discriminative ability among polymorphs than near-infrared spectroscopy and conventional Raman spectroscopy (200–1800 cm −1 ), was investigated as a possible application to PAT. This is because LF-Raman spectroscopy obtains information about intermolecular and/or lattice vibrations in the solid state. The monitoring results obtained from Furosemide/Nicotinamide cocrystal indicate that LF-Raman spectroscopy is applicable to in situ monitoring of suspension and fluidized bed granulation processes, and is an effective technique as a PAT tool to detect the conversion risk of cocrystals. LF-Raman spectroscopy is also used as a PAT tool to monitor reactions, crystallizations, and manufacturing processes of drug substances and products. In addition, a sequence of conversion behaviors of Furosemide/Nicotinamide cocrystals was determined by performing in situ monitoring for the first time. [ABSTRACT FROM AUTHOR]

This study considers the potential of low-frequency (terahertz) Raman spectroscopy in the quantitative analysis of ternary mixtures of solid-state forms. Direct comparison between low-frequency and mid-frequency spectral regions for quantitative analysis of crystal form mixtures, without confounding sampling and instrumental variations, is reported for the first time. Piroxicam was used as a model drug, and the low-frequency spectra of piroxicam forms β, α2 and monohydrate are presented for the first time. These forms show clear spectral differences in both the low- and mid-frequency regions. Both spectral regions provided quantitative models suitable for predicting the mixture compositions using partial least squares regression (PLSR), but the low-frequency data gave better models, based on lower errors of prediction (2.7, 3.1 and 3.2% root-mean-square errors of prediction [RMSEP] values for the β, α2 and monohydrate forms, respectively) than the mid-frequency data (6.3, 5.4 and 4.8%, for the β, α2 and monohydrate forms, respectively). The better performance of low-frequency Raman analysis was attributed to larger spectral differences between the solid-state forms, combined with a higher signal-to-noise ratio. [ABSTRACT FROM AUTHOR]

The hydrogen-bonding interactions in protic and aprotic amide solvent mixtures, i.e., formamide (FA) and N , N -dimethylformamide (DMF), were investigated via low-frequency Raman spectroscopy, small-angle neutron scattering (SANS) experiments, and molecular dynamics (MD) simulations. In a neat amide system, the low-frequency Raman spectra R ( ν )s were well reproduced by the corresponding S ( ν ) spectra derived from the MD simulations. The observed peaks in R ( ν )s at around < 200 cm − 1 were assigned to the intermolecular interactions, particularly in terms of the hydrogen-bonding network formation and its dimensionality in the liquid state. The SANS experiments for the FA–DMF mixtures demonstrated that the FA molecules forming an extended three–dimensional hydrogen-bonding structure in the neat system interacted with DMF molecules through the hydrogen bonds in the mixtures over the whole range of solvent compositions, resulting in a homogeneous mixing state. Additionally, the R ( ν ) spectra for the mixtures were represented by the corresponding S ( ν ) spectra. From the R ( ν ) and S ( ν ) spectra of the FA–DMF mixtures, we found that (1) the Raman band at around 110 cm − 1 mainly originates from the libration mode of amide molecules in the chain-like hydrogen-bonded structure and (2) the higher frequency band (approximately 200 cm − 1 ) was attributed to the libration of the FA molecule restricted by the three-dimensional hydrogen-bonded network, which remained even in the DMF-rich compositions. [ABSTRACT FROM AUTHOR]

The success rate for drug discovery and the development of innovative therapeutic strategies are intimately related to the physical properties of the solid-state condensed matter, which have direct influence on the bioavailability of Active Pharmaceutical Ingredients. In order to transform a new molecule in efficient drug, the material is brought into an amorphous state using various manufacturing processes including freeze drying, spray drying, hot melt extrusion and loading in different delivery devices. The infrared and Raman spectroscopic analyses used for exploring disordered and amorphous states, for the monitoring of the drug physical stability in drug delivery systems are described in this review. [ABSTRACT FROM AUTHOR]

van der Waals homo- and heterostructures assembled by stamping monolayers together present optoelectronic properties suitable for diverse applications. Understanding the details of the interlayer stacking and resulting coupling is crucial for tuning these properties. We investigated the low-frequency interlayer shear and breathing Raman modes (<50 cm-1) in twisted bilayer MoS2 by Raman spectroscopy and first-principles modeling. Twisting significantly alters the interlayer stacking and coupling, leading to notable frequency and intensity changes of low-frequency modes. The frequency variation can be up to 8 cm-1 and the intensity can vary by a factor of ~5 for twisting angles near 0° and 60°, where the stacking is a mixture of high-symmetry stacking patterns and is thus sensitive to twisting. For twisting angles between 20° and 40°, the interlayer coupling is nearly constant because the stacking results in mismatched lattices over the entire sample. It follows that the Raman signature is relatively uniform. Note that for some samples, multiple breathing mode peaks appear, indicating nonuniform coupling across the interface. In contrast to the low-frequency interlayer modes, high-frequency intralayer Raman modes are much less sensitive to interlayer stacking and coupling. This research demonstrates the effectiveness of low-frequency Raman modes for probing the interfacial coupling and environment of twisted bilayer MoS2 and potentially other two-dimensional materials and heterostructures. [ABSTRACT FROM AUTHOR]