Carbonyl Stretch Research Articles

Characterization and Cytotoxicity Assessment of Synthesized Palladium (II) Complex-Encapsulated Zinc Oxide Nanoparticles for Cancer Treatment.

The treatment of cancer often leads to a range of adverse effects. Encapsulating drugs can mitigate these effects and enhance drug efficacy by enabling a controlled release at the site of interest. This study details the successful synthesis of zinc oxide nanoparticles (ZnONPs) through the precipitation of Zn(NO3)2·6H2O with KOH. A Pd(II) complex drug was synthesized from a Schiff base ligand derived from 2-hydroxybenzohydrazide and (E)-1-(2-(p-tolyl)hydrazono)propan-2-one using potassium tetrachloropalladate(II). This complex was subsequently incorporated into ZnONPs. Characterization of the resulting compounds was performed using Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), Zeta Potential, Fourier Transform Infrared (FTIR) Spectroscopy, and UV-visible spectroscopy. TEM imaging revealed particle sizes of 160.69 ± 4.74 nm for ZnONPs and 185.28 ± 2.3 nm for the Pd(II) complex-encapsulated ZnONPs. The Zeta potential values were 6.53 mV for ZnONPs and 7.36 mV for Pd(II) complex-encapsulated ZnONPs. UV-visible spectroscopy showed an absorption peak at 360 nm for ZnONPs, while the Pd(II) complex-encapsulated ZnONPs exhibited a peak at 410 nm. FTIR analysis indicated the presence of the Pd(II) complex within the ZnONPs, as evidenced by a consistent Zn-O vibrational band at 832 cm-1 and a shift in another peak from 460 to 413 cm-1. Additionally, the detection of a C = N stretching vibration at 1548 cm-1 and a carbonyl stretch at 1626 cm-1 was observed. The Encapsulation Efficiency (E.E.) of the Pd(II) complex was 97.2%. A drug release experiment conducted at pH 7 showed a steady-state release pattern after 16 h, with a cumulative release of 44.3%. The cytotoxic effects of the Pd(II) complex and its encapsulated form in ZnONPs on the MCF-7 cell line were assessed via MTT test. The Pd(II) complex encapsulated within ZnONPs exhibited decreased toxicity relative to the unencapsulated drug, as evidenced by a higher IC50 value of 418.5 μg/ml. This suggests that the encapsulation facilitates a sustained release, which allows for targeted accumulation within cells. The elevated IC50 value indicates that the drug delivery system may be engineered to modulate the release of the drug in a more controlled manner, potentially resulting in a prolonged release profile rather than an immediate therapeutic impact.

Synthesis, characterization and antimicrobial evaluation of quaternary ammonium compounds from natural oils

Quaternary ammonium salts refer to any class of salt derived from ammonium in which the nitrogen atom is attached to four organic groups covalently, as in benzalkonium chloride (R4N+). Quaternary ammonium compounds were synthesized from Canola oil (Brasssicanapus) and Coconut oil (Cocos nucifera) extracts by reacting the oils with N,N-diethylethylenediamine in the presence of potassium tertiary butoxide as catalyst. Fourier Transform Infrared (FTIR) Spectrometric analyses of the starting materials, the intermediates and the final products were conducted, the results showed a disappearance of the carbonyl (C=O) stretch of an ester (the oil) at 1744cm-1 and appearance of N-H band of an amide at 3433cm-1, which resulted from the quaternization of benzyl chloride with the intermediates for both oils. Other functional groups such as C=C and C-H stretch of aromatic compound, C=O stretch of an amide were also observed.Mass spectrometric analysis of the final products were conducted and results showed the Molecular Ion peak (M+) which is the molecular weights of the products. Vital fragments such as base peaks were observed for both quats, other fragmented radical cations were observed.Antimicrobial activity of the synthesized Quaternary ammonium compounds (QACs) exhibited excellent anti-bacterial activity covering a diameter of 22 mm and 28 mm of E. coli for QACs from Cocos nucifera and Brassic anapus oils respectively as compared to the standard antibiotic (Ampillicin).

Tensile Control of Vibrational Strong Light‐Matter Coupling with Flexible Polyester Films

AbstractPolaritons are generated by strong interaction between photons and matter, with the hybridization fundamentally changing the energy landscape of the system. Future exploitation of polaritons will benefit from implementing low‐cost, flexible, and easily tuneable configurations, as electronics have before. Here, coherent coupling of the carbonyl stretch vibrations of polyester (poly(ethylene terephthalate), PET) films to the optical modes of a Fabry–Perot (FP) cavity is presented, in which the FP cavity is directly formed on flexible, free‐standing, and commercially available PET films. For 2‐µm thick PET films, the carbonyl stretch vibration of the PET overlaps with the half‐wavelength FP cavity mode, leading to the coupling of the two modes, a Rabi splitting above 160 cm−1, and associated anticrossing in angular dispersion measurements. The study demonstrates dynamic control of light‐matter interaction strength by modulating film thickness under tension, finding that a 25% tensile stretch can tune the light‐matter interaction from 20:80 mixing to near‐perfect 50:50 hybridization at normal incidence. These findings are discussed in the context of future foldable/twistable/wearable polaritonic devices.

Subradiant plasmonic cavities make bright polariton states dark

Abstract Nanostructured plasmonic surfaces allow for precise tailoring of electromagnetic modes within sub-diffraction mode volumes, boosting light–matter interactions. This study explores vibrational strong coupling (VSC) between molecular ensembles and subradiant “dark” cavities that support infrared quadrupolar plasmonic resonances (QPLs). The QPL mode exhibits a dispersion characteristic of bound states in the continuum (BIC). That is, the mode is subradiant or evanescent at normal incidence and acquires increasing “bright” dipole character with larger in-plane wavevectors. We deposited polymethyl methacrylate (PMMA) thin films on QPL substrates to induce VSC with the carbonyl stretch in PMMA and measured the resulting infrared (IR) spectra. Our computational analysis predicts the presence of “dark” subradiant polariton states within the near-field of the QPL mode, and “bright” collective molecular states. This finding is consistent with classical and quantum mechanical descriptions of VSC that predict hybrid polariton states with cavity-like modal character and N−1 collective molecular states with minimal cavity character. However, the behaviour is opposite of what is standardly observed in VSC experiments that use “bright” cavities, which results in “bright” polariton states that can be spectrally resolved as well as N−1 collective molecular states that are spectrally absent. Our experiments confirm a reduction of molecular absorption and other spectral signatures of VSC with the QPL mode. In comparison, our experiments promoting VSC with dipolar plasmonic resonances (DPLs) reproduce the conventional behavior. Our results highlight the significance of cavity mode symmetry in modifying the properties of the resultant states from VSC, while offering prospects for direct experimental probing of the N−1 molecule-like states that are usually spectrally “dark”.

Investigation of antimicrobial and anti-cancer activity of thermally sensitive SnO2 nanostructures with green-synthesized cauliflower morphology at ambient weather conditions

A tin oxide (SnO2) nanostructure was prepared using Matricaria recutita leaf extract to investigate its anticancer activity against SK-MEL-28 cells. The tetragonal crystal structure of tin oxide nanoparticles with an average crystal size of 27 nm was confirmed by X-ray diffraction (XRD) analysis. The tetragonal crystal structure of the tin oxide nanoparticles, with an average crystallite size of 27 nm, was confirmed by XRD an absorbance peak at 365 nm was identified by UV–visible spectroscopy analysis as belonging to the bio-mediated synthesis of SnO2 nanoparticles. The SnO2 NPs are capped and stabilized with diverse functional groups derived from bioactive molecules, including aldehydes, benzene rings, amines, alcohols, and carbonyl stretch protein molecules. Fourier transform infrared spectroscopy (FTIR) analysis validated the presence of these capping and stabilizing chemical bonds. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies revealed the cauliflower-shaped morphology of the SnO2 nanoparticles with an average particle size of 28 nm. The antimicrobial activity of both prepared and encapsulated samples confirmed their biological activities. Furthermore, both prepared and encapsulated tin oxide samples exhibited excellent anticancer activity against SK-MEL-28 human cancer cells. The present study introduces a reliable and uncomplicated approach to produce SnO2 nanoparticles and demonstrates their effectiveness in various applications, including cancer therapy, drug administration, and disinfectant.

Multimode vibrational strong coupling in direct laser written mid-IR plasmonic MIM nano-patch antennas

Strong coupling of mid-infrared (mid-IR) vibrational transitions to optical cavities provides a means to modify and control a material’s chemical reactivity and offers a foundation for novel chemical detection technology. Currently, the relatively large volumes of the mid-IR photonic cavities and weak oscillator strengths of vibrational transitions restrict vibrational strong coupling (VSC) studies and devices to large ensembles of molecules, thus representing a potential limitation of this nascent field. Here, we experimentally and theoretically investigate the mid-IR optical properties of 3D-printed multimode metal–insulator–metal (MIM) plasmonic nanoscale cavities for enabling strong light–matter interactions at a deep subwavelength regime. We observe strong vibration-plasmon coupling between the two dipolar modes of the L-shaped cavity and the carbonyl stretch vibrational transition of the polymer dielectric. The cavity mode volume is half the size of a typical square-shaped MIM geometry, thus enabling a reduction in the number of vibrational oscillators to achieve strong coupling. The resulting three polariton modes are well described by a fully coupled multimode oscillator model where all coupling potentials are non-zero. The 3D printing technique of the cavities is a highly accessible and versatile means of printing arbitrarily shaped submicron-sized mid-IR plasmonic cavities capable of producing strong light–matter interactions for a variety of photonic or photochemical applications. Specifically, similar MIM structures fabricated with nanoscopic voids within the insulator region could constitute a promising microfluidic plasmonic cavity device platform for applications in chemical sensing or photochemistry.

Ultrafast transient vibrational action spectroscopy of cryogenically cooled ions.

Ultrafast transient vibrational action spectra of cryogenically cooled Re(CO)3(CH3CN)3+ ions are presented. Nonlinear spectra were collected in the time domain by monitoring the photodissociation of a weakly bound N2 messenger tag as a function of delay times and phases between a set of three infrared pulses. Frequency-resolved spectra in the carbonyl stretch region show relatively strong bleaching signals that oscillate at the difference frequency between the two observed vibrational features as a function of the pump-probe waiting time. This observation is consistent with the presence of nonlinear pathways resulting from underlying cross-peak signals between the coupled symmetric-asymmetric C≡O stretch pair. The successful demonstration of frequency-resolved ultrafast transient vibrational action spectroscopy of dilute molecular ion ensembles provides an exciting, new framework for the study of molecular dynamics in isolated, complex molecular ion systems.

Modification of ground-state chemical reactivity via light-matter coherence in infrared cavities.

Reaction-rate modifications for chemical processes due to strong coupling between reactant molecular vibrations and the cavity vacuum have been reported; however, no currently accepted mechanisms explain these observations. In this work, reaction-rate constants were extracted from evolving cavity transmission spectra, revealing resonant suppression of the intracavity reaction rate for alcoholysis of phenyl isocyanate with cyclohexanol. We observed up to an 80% suppression of the rate by tuning cavity modes to be resonant with the reactant isocyanate (NCO) stretch, the product carbonyl (CO) stretch, and cooperative reactant-solvent modes (CH). These results were interpreted using an open quantum system model that predicted resonant modifications of the vibrational distribution of reactants from canonical statistics as a result of light-matter quantum coherences, suggesting links to explore between chemistry and quantum science.

Biocompatible Poly(Vinyl Alcohol)-Copper Oxide-Graphene Oxide (PVA-CuO-GO) Nanocomposites: Synthesis, Structural and Optical Properties

Motivated by the unique combination of copper oxide (CuO) and GO (graphene oxide) nano-fillers with optimized composition in the PVA (poly vinyl alcohol) polymer, the studies in this paper have been directed towards the synthesis and characterization of (PVA-CuO-GO) polymer nanocomposites. The polymer nanocomposites, i.e., PVA-CuO-GO have been prepared by melt blending technique considering GO and CuO with variable wt.% (ranging from 0.5 to 3 wt.%). The composite was made in the shape of a dumble-like structure. To get the structural information, optical properties, surface morphology and available functional groups in the composites and their mechanisms, XRD (x-ray diffraction), UV-Vis-NIR spectrophotometer, photoluminescence (PL), FESEM (field emission scanning electron microscope) and FTIR (Fourier transform infrared) techniques have been used, respectively. From XRD data, the effect of wt.% of nano-fillers on crystalline size and micro-strain has been studied. The average crystalline size and micro-strain were calculated as ∼32 nm and ∼0.0250, respectively. From UV-Vis-NIR spectrophotometer data, tauc plots have been studied which tells that the increment in wt.% of nano-fillers causes the optical band gap to increase. On increasing the concentration of nano-fillers from 0.5 to 3 wt.%, the bandgap was increased from 2.5 to 2.8 eV. This tuning of bandgap can be supposed as fine tuning in near UV region. According to PL results, all the composites show a wide emission band in the UV-Vis region with the maximum at 487 nm when excited by 415 nm wavelength. Further, the luminescence intensity has been found to decrease with the addition of wt.% of the loading. The smoothness of the surfaces of the composites has also been studied with EDAX analysis. According to FTIR spectra, the available functional groups were found as: C–O, C–H stretch, C–H asymmetric stretch, C=O carbonyl stretch and C–H bending and deformation vibrations. In view of the characterizing results, the synthesized polymer nanocomposites can be used in several kinds of optoelectronics applications.

Ground-state heterogeneity and vibrational energy redistribution in bacterial phytochrome observed with femtosecond 2D IR spectroscopy.

Phytochromes belong to a group of photoreceptor proteins containing a covalently bound biliverdin chromophore that inter-converts between two isomeric forms upon photoexcitation. The existence and stability of the photocycle products are largely determined by the protein sequence and the presence of conserved hydrogen-bonding interactions in the vicinity of the chromophore. The vibrational signatures of biliverdin, however, are often weak and obscured under more intense protein bands, limiting spectroscopic studies of its non-transient signals. In this study, we apply isotope-labeling techniques to isolate the vibrational bands from the protein-bound chromophore of the bacterial phytochrome from Deinococcus radiodurans. We elucidate the structure and ultrafast dynamics of the chromophore with 2D infra-red (IR) spectroscopy and molecular dynamics simulations. The carbonyl stretch vibrations of the pyrrole rings show the heterogeneous distribution of hydrogen-bonding structures, which exhibit distinct ultrafast relaxation dynamics. Moreover, we resolve a previously undetected 1678cm-1 band that is strongly coupled to the A- and D-ring of biliverdin and demonstrate the presence of complex vibrational redistribution pathways between the biliverdin modes with relaxation-assisted measurements of 2D IR cross peaks. In summary, we expect 2D IR spectroscopy to be useful in explaining how point mutations in the protein sequence affect the hydrogen-bonding structure around the chromophore and consequently its ability to photoisomerize to the light-activated states.

Vibrational relaxation by methylated xanthines in solution: Insights from 2D IR spectroscopy and calculations.

Two-dimensional infrared (2D IR) spectroscopy, infrared pump-infrared probe spectroscopy, and density functional theory calculations were used to study vibrational relaxation by ring and carbonyl stretching modes in a series of methylated xanthine derivatives in acetonitrile and deuterium oxide (heavy water). Isotropic signals from the excited symmetric and asymmetric carbonyl stretch modes decay biexponentially in both solvents. Coherent energy transfer between the symmetric and asymmetric carbonyl stretching modes gives rise to a quantum beat in the time-dependent anisotropy signals. The damping time of the coherent oscillation agrees with the fast decay component of the carbonyl bleach recovery signals, indicating that this time constant reflects intramolecular vibrational redistribution (IVR) to other solute modes. Despite their similar frequencies, the excited ring modes decay monoexponentially with a time constant that matches the slow decay component of the carbonyl modes. The slow decay times, which are faster in heavy water than in acetonitrile, approximately match the ones observed in previous UV pump-IR probe measurements on the same compounds. The slow component is assigned to intermolecular energy transfer to solvent bath modes from low-frequency solute modes, which are populated by IVR and are anharmonically coupled to the carbonyl and ring stretch modes. 2D IR measurements indicate that the carbonyl stretching modes are weakly coupled to the delocalized ring modes, resulting in slow exchange that cannot explain the common solvent-dependence. IVR is suggested to occur at different rates for the carbonyl vs ring modes due to differences in mode-specific couplings and not to differences in the density of accessible states.

IR spectra and structures of saturated ruthenium cluster carbonyl cations Run(CO)m+ (n = 1-6).

A series of saturated ruthenium cluster carbonyls (Ru(CO)5+, Ru2(CO)9+, Ru3(CO)12+, Ru4(CO)14+, Ru5(CO)16+ and Ru6(CO)18+) have been synthesized in the gas phase and subsequently characterized by infrared spectroscopy. Their size-specific IR spectra in the region of the carbonyl stretch vibration (1900-2150 cm-1) and in the region of the Ru-C-O bending modes (420-620 cm-1) are obtained by infrared multiple photon dissociation spectroscopy. The structures of these cluster carbonyls are assigned by comparison with results from density functional calculations. A multitude of differently activated CO ligands are identified in these cationic cluster carbonyls, reaching from terminal, over non-symmetrically bridging (semi-bridging) ligands with varying degrees of interaction to additional Ru atoms towards symmetrically bridging CO ligands.

Ultrafast Two-Dimensional Infrared Spectroscopy Resolved a Structured Lysine 159 on the Cytoplasmic Surface of the Microbial Photoreceptor Bacteriorhodopsin.

Bacteriorhodopsin (bR) is a light-driven microbial receptor, and lysine 159 (K159) is a charged residue on the cytoplasmic (CP) side of its E-F loop. However, its conformation and function remain unknown due to fast surface dynamics. By utilizing a 13C, 15N-labeled lysine (K) as an isotope probe, we created a network of site-specific amide-I vibrational signatures (backbone carbonyl stretch) to identify the frequency contribution of the labeled residues to the amide-I excitonic band structure. Thus, the red-shifted amide-I frequency in the 13C, 15N-lysine-labeled bR (uK-bR) to the unlabeled bR (WT-bR) could be differentiated and examined by ultrafast two-dimensional vibrational echo infrared (2D IR) spectroscopy. Our results showed that the backbone carbonyl of K159 is located at a high frequency of ca. 1693 cm-1 and has a vibrational excited-state relaxation time shorter than the bulk helical amide-I mode at the same frequency, suggesting that K159 may possess a hydrogen-bonded γ-turn structure with E161, one of the carboxylate residues on the CP surface of bR. The 2D solid-state NMR study of uK-bR also revealed conformational dependent lysine residues, from which K159 was found to involve the turn motif. This γ-turn structure maintained by K159 may help to stabilize the E-F loop and support E161 in attracting protons from the bulk during the late stage of the bR photocycle. The combined spectroscopic approach illustrated in this work may be applied to map residue-specific local structures and dynamics of other receptors and large proteins.

Synthesis and Characterization of a Novel Composite Scaffold Based on Hyaluronic Acid and Equine Type I Collagen.

Herein, the synthesis and characterization of a novel composite biopolymer scaffold—based on equine type I collagen and hyaluronic acid—were described by using a reaction in heterogeneous phase. The resulting biomimetic structure was characterized in terms of chemical, physical, and cytotoxicity properties using human-derived lymphocytes and chondrocytes. Firstly, FT-IR data proved a successful reticulation of hyaluronic acid within collagen structure with the appearance of a new peak at a wavenumber of 1735 cm−1 associated with ester carbonyl stretch. TGA and DSC characterizations confirmed different thermal stability of cross-linked scaffolds while morphological analysis by scanning electron microscopy (SEM) suggested the presence of a highly porous structure with open and interconnected void areas suitable for hosting cells. The enzymatic degradation profile confirmed scaffold higher endurance with collagenase as compared with collagen alone. However, it was particularly interesting that the mechanical behavior of the composite scaffold showed an excellent shape memory, especially when it was hydrated, with an improved Young’s modulus of 9.96 ± 0.53 kPa (p ≤ 0.001) as well as a maximum load at 97.36 ± 3.58 kPa compared to the simple collagen scaffold that had a modulus of 1.57 ± 0.08 kPa and a maximum load of 36.91 ± 0.24 kPa. Finally, in vitro cytotoxicity confirmed good product safety with human lymphocytes (viability of 81.92 ± 1.9 and 76.37 ± 1.2 after 24 and 48 h, respectively), whereas excellent gene expression profiles of chondrocytes with a significant upregulation of SOX9 and ACAN after 10 days of culture indicated our scaffold’s ability of preserving chondrogenic phenotype. The described material could be considered a potential tool to be implanted in patients with cartilage defects.

Autotuning of Vibrational Strong Coupling for Site-Selective Reactions.

Site-selective chemistry opens new paths for the synthesis of technologically important molecules. When a reactant is placed inside a Fabry-Perot (FP) cavity, energy exchange between molecular vibrations and resonant cavity photons results in vibrational strong coupling (VSC). VSC has recently been implicated in modified chemical reactivity at specific reactive sites. However, as a reaction proceeds inside an FP cavity, the refractive index of the reaction solution changes, detuning the cavity mode away from the vibrational mode and weakening the VSC effect. Here we overcome this issue, developing actuatable FP cavities to allow automated tuning of cavity mode energy to maintain maximized VSC during a reaction. As an example, the site-selective reaction of the aldehyde over the ketone in 4-acetylbenzaldehyde is achieved by automated cavity tuning to maintain optimal VSC of the ketone carbonyl stretch during the reaction. A nearly 50 % improvement in site-selective reactivity is observed compared to an FP cavity with static mirrors, demonstrating the utility of actuatable FP cavities as microreactors for organic chemistry.

Production and characterization of polyhydroxybutyrate (PHB) BY Burkholderia cepacia BPT1213 using waste glycerol as carbon source

This study focused on the utilization of waste glycerol, a by-product of the biodiesel industry, used as a carbon source to grow Burkholderia cepacia BPT1213 for the production of PHB. B. cepacia BPT1213 was cultivated in minimal salt media (MSM) supplemented with waste glycerol at concentrations ranging from 2% to 9% (v/v). A gradual decrease was depicted by the cell dry weight (CDW) and PHB content with increasing waste glycerol content. B. cepacia BPT1213 is able to synthesize and accumulate up to 2.41 g/L and 66.4% dry biomass and PHB yield respectively when supplemented with 2% (v/v) waste glycerol. This resulted in a total PHB concentration of 1.6 g/L. The characterization of extracted PHB was carried out by Nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) for structural composition evaluation. Both analyses showed expected signals for PHB as reported in other studies which depicted the methyl, methylene and methine groups for NMR analyses, and certain functional groups which were the hydroxyl group, carbonyl stretch and ester group for FTIR. This study demonstrated the effects of waste glycerol concentration on the end properties of PHB, which is an important aspect for its applications.

Polyhydroxybutyrate production by Chlorella sorokiniana SVMIICT8 under Nutrient-deprived mixotrophy

Polyhydroxybutyrates (PHBs) are naturally occurring biopolymeric compounds that accumulate in a variety of microorganisms, including microalgae as energy and carbon storage sources. The present study was designed to evaluate nature-based PHB production using microalgae (Chlorella sorokiniana SVMIICT8) in biphasic (growth (GP) and stress phase (SP)) nutritional mode of cultivation. Microalgal PHB accumulation was driven by nutrient constraint, with a maximal production of 29.5% of PHB from 0.94 gm L−1 of biomass. Fluorescence microscopy revealed PHB granules in the cell cytoplasm, while NMR (1H and 13C), XRD and TGA analysis confirmed the structure. The biopolymer obtained was homopolymer of PHB with carbonyl (C=O) stretch of the aliphatic ester moiety. In GC-MS analysis, major peak representing butyric acid methyl ester also confirmed the PHB. Chlorophyll a fluorescence transients inferred through OJIP, exhibited significant variation in photosynthetic process during growth and nutrient limiting conditions. Mining of bio-based products from microalgae cultivation embrace nature-based approach addressing climate change and sustainability inclusively.

Vibrational Strong Light–Matter Coupling in an Open Microcavity Based on Reflective Germanium Coatings

Open microcavities (OMCs) enable tuning of the optical resonances of a system and insertion of different materials between the mirrors. They are of large scientific interest due to their many potential applications. Using OMCs, we can observe strong light-matter coupling while tuning the cavity wavelength. Typically, dielectric Bragg reflectors (DBRs) and Au mirrors are used to form microcavities and observe vibrational strong coupling (VSC) in the middle-infrared (MIR) spectral region. Here, we make the mirrors of the OMC using thin film coatings of the semiconducting material germanium (Ge) and demonstrate VSC in the MIR region. We deposited a uniform coating of poly(methyl methacrylate) (PMMA) on one of the OMC mirrors' inner surfaces, and then we tuned the cavity to the carbonyl stretch mode resonance at 1731 cm-1. Comparing VSC using Ge mirrors to DBRs or Au mirrors, we achieve enhanced optical transmission through the polaritonic resonances and large Rabi splitting, with Rabi-splitting values of 8.8 meV for the Ge mirror-based OMC compared to 7.0 and 7.4 meV for the DBR- and Au-based microcavities, respectively. The use of Ge mirror components can simplify the microcavity structure and offer a new and simple alternative for MIR semiconductor mirrors, which may be particularly useful for polariton chemistry applications.

Fungi fabrication, characterization, and anticancer activity of silver nanoparticles using metals resistant Aspergillus niger

The purpose of this study was to assess the bio-fabrication possibilities of pre-isolated (from bauxite mine tailings) metal-tolerant Aspergillus niger biomass filtrate and the anticancer potential of synthesized silver nanoparticles (AgNPs) tested with a Human Cervical cancer cell line (HeLa cells: Henrietta Lacks cells). The nitrate reduction test demonstrated that A. niger has the ability to reduce nitrate, and filtrate derived from A. niger biomass efficiently fabricated AgNPs from AgNO3, as demonstrated by a visible color change from pale greenish to brownish. The UV–visible spectroscopy analysis revealed an absorbance peak at 435 nm, which corresponded to the AgNPs. These AgNPs have been capped and stabilized with several functional groups related to various bioactive molecules such as aldehyde, benzene rings, aldehydic, amines, alcohols, and carbonyl stretch protein molecules. Fourier-Transform Infrared Spectroscopy (FTIR) analysis confirmed the capping and stabilizing chemical bonding pattern. Scanning Electron Microscopy (SEM) revealed that the synthesized AgNPs were spherical, with an average size of 21.38 nm. This bio-fabricated AgNPs has in-vitro anticancer potential when tested against the HeLa cell line due to its potential size and shape. At 100 g mL−1 concentrations of this bio-fabricated AgNPs, the anticancer activity percentage was found to be 70.2%, and the IC50 value was found to be 66.32 g m−1. These findings demonstrated that the metal-tolerant A. niger cell filtrate could produce AgNPs with anticancer potential.

Bulk Response of Carboxylic Acid Solutions Observed with Surface Sum-Frequency Generation Spectroscopy.

We study the molecular properties of aqueous acetic acid and formic acid solutions with heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). For acid concentrations up to ∼5 M, we observe a strong increase of the responses of the acid hydroxyl and carbonyl stretch vibrations with increasing acid concentration due to an increase of the surface coverage by the acid molecules. At acid concentrations >5 M we observe first a saturation of these responses and then a decrease. For pure carboxylic acids we even observe a change of sign of the Im[χ(2)] response of the carbonyl vibration. The decrease of the response of the hydroxyl vibration and the decrease and sign change of the response of the carbonyl vibration indicate the formation of cyclic dimers, which only show a quadrupolar bulk response in the HD-VSFG spectrum because of their antiparallel conformation. We also find evidence for the presence of a quadrupolar response of the CH vibrations of the acid molecules.