Identification of microplastics using Raman spectroscopy: latest developments and future prospects

Widespread microplastic pollution is raising growing concerns as to its detrimental effects upon living organisms. A realistic risk assessment must stand on representative data on the abundance, size distribution and chemical composition of microplastics. Raman microscopy is an indispensable tool for the analysis of very small microplastics (<20 μm). Still, its use is far from widespread, in part due to drawbacks such as long measurement time and proneness to spectral distortion induced by fluorescence. This review discusses each drawback followed by a showcase of interesting and easily available solutions that contribute to faster and better identification of microplastics using Raman spectroscopy. Among discussed topics are: enhanced signal quality with better detectors and spectrum processing; automated particle selection for faster Raman mapping; comprehensive reference libraries for successful spectral matching. A last section introduces non-conventional Raman techniques (non-linear Raman, hyperspectral imaging, standoff Raman) which permit more advanced applications such as real-time Raman detection and imaging of microplastics.publishe

Evidence of C−H···O Hydrogen Bonds in Liquid 4-Ethoxybenzaldehyde by NMR and Vibrational Spectroscopies

Raman, FTIR, and NMR (both 13C and 17O) spectroscopies are used in a complementary way in order to study the occurrence of C−H···O intermolecular hydrogen bonds in liquid 4-ethoxybenzaldehyde (4EtOB). Additional information concerning the structure of the possible dimers is obtained through ab initio calculations, at the B3LYP/6-31G* level. The strongest evidences of the presence of C−H···O hydrogen bonds in the liquid phase arise from the temperature and solvent intensity dependence of the two bands observed in the νCO region of the vibrational spectra, as well as from the shift to low magnetic field detected for the carbonyl 17O NMR peak at higher dilutions. Further evidence is gathered from the changes observed in the νC-H vibrational modes, the 1JCH concentration dependence detected in the NMR spectra, and ab initio results. The experimental observations are consistent with the decrease of the C−H bond length upon hydrogen-bonding, as predicted for the nonstandard blue-shifting hydrogen bonds. Ab initio calculations predict several possible structures for the dimeric species, with nearly identical energies. The calculated dimerization energy is within the −5.1 to −6.5 kJ mol-1 range, considering both basis set superposition error and zero-point vibrational energy corrections, in agreement with the obtained experimental ΔH value of −5.7 ± 0.5 kJ mol-1

Análise comparativa dos ficocolóides produzidos por algas carragenófitas usadas industrialmente e algas carragenófitas portuguesas

As Carragenanas (E-407) constituem um dos principais aditivos usados pela indústria alimentar, como agentes gelificantes, emulsionantes, estabilizantes e espessantes. São ingredientes naturais, usados há várias décadas na área alimentar e são considerados como seguros, tendo obtido a classificação GRAS (Generally Recognised As Safe). Neste trabalho foram analisadas a percentagem de peso seco e a composição química (por FTIR e FT-Raman) das carragenanas produzidas pelas carragenófitas (Gigartinales, Rhodophyta) oriundas de diversos países: Kappaphycus alvarezzi (Tanzânia, Indonésia, Filipinas); Kappaphycus striatum (Madagáscar); Eucheuma denticulatum (Tanzânia, Filipinas e Madagáscar); Betaphycus gelatinum (Filipinas); e Sarcothalia crispata (Chile). Para comparação foram também analisadas algas carragenófitas da costa portuguesa (Gigartinales, Rhodophyta): Chondrus crispus, Mastocarpus stellatus; Gigartina pistillata; Chondracanthus teedei var. lusitanicus; Chondracanthus acicularis; Calliblepharis jubata; Gymnogongrus crenulatus; e Ahnfeltiopsis devoniensis. Os principais resultados a reter são: a maior percentagem de peso seco em carragenanas foi obtida a partir das algas carragenófitas Kappaphycus alvarezzi (Filipinas), com 84.4% e Gigartina pistillata (Praia do Norte, Viana do Castelo), com 65.4%. Relativamente à natureza dos ficocolóides produzidos pelas carragenófitas estudadas, as nossas análises espectroscópicas permitiram determinar a presença de um leque diversificado de carragenanas: carragenana iota pura; carragenana kappa quase pura; uma série de carragenanas híbridas kappa-iota, com diferentes rácios iota/kappa; carragenanas kappa-beta, xi-tetha e xi-lambda

VIBRATIONAL SPECTROSCOPY (FTIR-ATR AND FT-RAMAN) - A Rapid and Useful Tool for Phycocolloid Analysis

The wide industrial application of phycocolloids (e.g. alginates, agar and carrageenans) is based on their particular properties to form gels in aqueous solution. Recently, new spectroscopic techniques have provided more accurate identification of the natural composition of the polysaccharides produced by these seaweeds. With the combination of two spectroscopic techniques (FTIR-ATR and FT-Raman) it is possible to identify the principal seaweed colloids in ground seaweed samples as in extracted material. Since the seaweed samples receive the minimum of handling and treatment (e.g. they are simply dried and ground), the composition determined represents, as accurately as possible, the native composition of the phycocolloids

Analysis by vibrational spectroscopy of seaweed polysaccharides with potential use in food, pharmaceutical and cosmetic industries

Polysaccharides present in several seaweeds (Kappaphycus alvarezii, Calliblepharis jubata, and Chondrus crispus—Gigartinales, Rhodophyta; Gelidium corneum and Pterocladiella capillacea—Gelidiales, Rhodophyta; Laurencia obtusa—Ceramiales, Rhodophyta; Himanthalia elongata, Undaria pinnatifida, Saccorhiza polyschides, Sargassum vulgare, and Padina pavonica—Phaeophyceae, Ochrophyta) are analyzed by spectroscopic techniques. The nature of the polysaccharides (with extraction and without any type of extraction) present in these seaweeds was determined with FTIR-ATR and FT-Raman analysis of extracted phycocolloids and ground dry seaweed

On the Relevance of Considering the Intermolecular Interactions on the Prediction of the Vibrational Spectra of Isopropylamine

The effects of implicitly considering the effects of hydrogen bonding on the molecular properties, such as vibrational frequencies, were inferred on the basis of DFT calculations. Several clusters of isopropylamine were assembled and theoretically characterized. The results showed that maximum H-bond cooperativity is achieved when the amine group acts simultaneously as donor and acceptor. The effect of H-bond cooperativity manifests itself in the relative cluster stability and on the structural and vibrational frequency predictions. Referring to the vibrational frequencies it was found that the NH2 stretching and torsion vibrational modes are the most affected by the amine involvement in hydrogen bonding. Both stretching modes were found to be significantly redshifted relative to the monomer. The NH2 torsional mode, on the other hand, was found to be blueshifted up to 350 cm(-1). Finally, the comparative study between the theory levels performed allows to conclude that the small 6-31G* basis set is able to stabilize weak C-H center dot center dot center dot N interactions as long as the new dispersion corrected DFT methods are considered. The impairments observed with conventional DFT methods for describing weak interactions may be overcome with the improvement of basis set, but the associated increase of computational costs may turn the calculations unfeasible

Tripyridinium cis-tetra­chlorido­dioxido­molybdate(VI) chloride

In the title compound, (C5H6N)3[MoCl4O2]Cl, the pyridinium cations are N—H⋯Cl hydrogen bonded to the anionic [MoCl4O2]2− complexes and to the two crystallographically independent chloride anions (located on C2 axes). The Mo6+ centre adopts a highly distorted octa­hedral geometry, being surrounded by four chloride and two terminal oxide groups. The oxide ligands are mutually cis

Tetra­pyridinium μ-oxido-di-μ-sulfato-bis­[chloridodioxidomolybdate(VI)]

The title salt, (C5H6N)4[Mo2Cl2O5(SO4)2], comprises four pyridinium cations for each [(MoClO2)2(μ-O)(μ-SO4)2]4− anionic unit. The asymmetric unit consists of three aggregates of the empirical formula. The tetra­anionic bimetallic molybdenum(VI) cluster is unprecedented and contains two sulfate and one oxide bridges. This structure constitutes the first example of a non-polymeric compound with terminal oxide, sulfate and halide ligands bonded to the same metal. The hydrogen bonds connecting the pyridinium cations to the molybdenum clusters are diverse, varying from strong and directional interactions to bifurcated bonds with a subsequent loss of directionality

(R)-(1-Ammonio­eth­yl)phospho­nate

The title compound, C2H8NO3P, crystallizes in its zwitterionic form H3N+CH(CH3)PO(O−)(OH). In the crystal, the molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds

Bis(μ-4-phenyl­pyridine N-oxide-κ2 O:O)bis­[bis­(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato)copper(II)]

The asymmetric unit of the title compound, [Cu2(C5HF6O2)4(C11H9NO)2], contains one half of the centrosymmetric dinuclear complex. The coordination geometry of the CuII atom is octa­hedral, exhibiting a typical Jahn–Teller distortion. One trifluoro­methyl group is rotationally disordered between two orientations in a 1:1 ratio