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Herein, we study the incorporation of hydrophilic-to-amphiphilic alkylated N-vinylimidazolium based ionic liquid monomers with different counter anions into N-vinylcaprolactam (VCL) based microgels via precipitation polymerization, and their resulting properties. Two strategies, following either a pre-functionalization of the comonomers by counterion exchange with subsequent polymerization, or post-functionalization via counterion exchange on pre-synthesized microgels, are applied and compared. The employed anions, i.e., halides (X-), methanesulfonate (MeS-), tetrafluoroborate (BF4-), and bistriflimide (NTf2-), were selected because of their kosmotropic-to-chaotropic solution properties. The resulting microgels with 10 mol% degree of functionalization were characterized by light scattering techniques, particularly with respect to their temperature-dependent swelling behavior and electrophoretic mobility. Differences in the counterion effect can be correlated to the solvation of the anions given by the Hofmeister series, cation-anion interaction strength, as well as the hydrophobicity of the vinylimidazolium moiety, i.e., the alkyl chain length. In this context, chaotropic anions will lead to a decrease in microgel size and electrophoretic mobility, while the volume phase transition temperature decreases as a function of the alkyl chain length. Moreover, the pre-functionalization approach can give access to different morphologies, such as anisotropic microgels, while generally restricting the microgel swelling, compared to the post-functionalization approach. Our results will allow for the controlled design of new functional microgels via simple precipitation polymerization with potential applications in drug delivery, biocatalysis and self-healing materials.

The third harmonic generation (THG) of graphite layers on paper substrate upon excitation with intense (up to 100 kV cm(-1)) narrowband terahertz (THz) pulses is studied. Highest THG efficiencies are comparable with those of chemical vapor deposition-grown single-layer graphene. Samples are hand drawn, using commercially available pencils. The THG response shows high sensitivity regarding the hatching direction relative to the THz polarization orientation. Using Raman spectroscopy, the occurrence of graphene-like structures in the samples is confirmed. The findings demonstrate the feasibility of virtually no-cost and easy-to-fabricate materials for THz nonlinear optics.

Purpose of review The aim of this review is to discuss recent studies on the assessment of tumor extension and resection margins by different intraoperative techniques allowing for image-guided surgery of oral cancer. Recent findings There are different in-vivo and ex-vivo intraoperative techniques to improve margin control of which intraoperative ultrasound and targeted fluorescence-guided resections have high potential clinical value and are closest to clinical implementation. In oral cancer surgery, resection margins, particularly deep margins, are often inadequate. Intraoperative frozen section does not improve resection margin control sufficiently. Specimen-driven intraoperative assessment for gross analysis of suspected margins reduces the amount of positive resection margins substantially but leaves still room for improvement. Mucosal staining methods, optical coherence tomography and narrow band imaging can only be used for superficial (mucosal) resection margin control. Spectroscopy is under investigation, but clinical data are scarce. Intraoperative ex-vivo imaging of the resection specimen by magnetic resonance and PET/computed tomography may be used to assess resection margins but needs more research. Intraoperative in-vivo ad ex-vivo ultrasound and targeted fluorescence imaging have high potential clinical value to guide oral cancer resections and are closest to clinical implementation for improved margin control.

A series of zigzag-edged polycyclic aromatic hydrocarbons (PAHs) (Z1-Z3) were synthesized from 2,12-dibromo-7,14-diphenyl-benzo[m]tetraphene (9) as a versatile building block. Their structures were unambiguously confirmed by laser desorption/ionization time-of-flight mass spectrometry, 1H NMR, Raman, and Fourier-transformed infrared (FTIR) spectroscopies as well as scanning tunneling microscopy. The fingerprint vibrational modes were elucidated with theoretical support. The edge- and size-dependent optical properties were characterized by UV-Vis absorption and fluorescence spectroscopy and DFT calculations. Moreover, ultrafast transient absorption spectroscopy revealed distinct modulation of the photophysical properties upon π-extension from Z1 to Z2, the latter having a gulf edge.

Purpose of review The aim of this review is to discuss recent studies on the assessment of tumor extension and resection margins by different intraoperative techniques allowing for image-guided surgery of oral cancer. Recent findings There are different in-vivo and ex-vivo intraoperative techniques to improve margin control of which intraoperative ultrasound and targeted fluorescence-guided resections have high potential clinical value and are closest to clinical implementation. In oral cancer surgery, resection margins, particularly deep margins, are often inadequate. Intraoperative frozen section does not improve resection margin control sufficiently. Specimen-driven intraoperative assessment for gross analysis of suspected margins reduces the amount of positive resection margins substantially but leaves still room for improvement. Mucosal staining methods, optical coherence tomography and narrow band imaging can only be used for superficial (mucosal) resection margin control. Spectroscopy is under investigation, but clinical data are scarce. Intraoperative ex-vivo imaging of the resection specimen by magnetic resonance and PET/computed tomography may be used to assess resection margins but needs more research. Intraoperative in-vivo ad ex-vivo ultrasound and targeted fluorescence imaging have high potential clinical value to guide oral cancer resections and are closest to clinical implementation for improved margin control.

Batteries employing transition-metal sulfides enable high-charge storage capacities, but polysulfide shuttling and volume expansion cause structural disintegration and early capacity fading. The design of heterostructures combining metal sulfides and carbon with an optimized morphology can effectively address these issues. Our work introduces dopamine-coated copper Prussian blue (CuPB) analogue as a template to prepare nanostructured mixed copper-iron sulfide electrodes. The material was prepared by coprecipitation of CuPB with in situ dopamine polymerization, followed by thermal sulfidation. Dopamine controls the particle size and favors K-rich CuPB due to its polymerization mechanism. While the presence of the coating prevents particle agglomeration during thermal sulfidation, its thickness demonstrates a key effect on the electrochemical performance of the derived sulfides. After a two-step activation process during cycling, the C-coated KCuFeS2electrodes showed capacities up to 800 mAh/g at 10 mA/g with nearly 100% capacity recovery after rate handling and a capacity of 380 mAh/g at 250 mA/g after 500 cycles.

Brain tumour identification and delineation in a timeframe of seconds would significantly guide and support surgical decisions. Here, treatment is often complicated by the infiltration of gliomas in the surrounding brain parenchyma. Accurate delineation of the invasive margins is essential to increase the extent of resection and to avoid postoperative neurological deficits. Currently, histopathological annotation of brain biopsies and genetic phenotyping still define the first line treatment, where results become only available after surgery. Furthermore, adjuvant techniques to improve intraoperative visualisation of the tumour tissue have been developed and validated. In this review, we focused on the sensitivity and specificity of conventional techniques to characterise the tumour type and margin, specifically fluorescent-guided surgery, neuronavigation and intraoperative imaging as well as on more experimental techniques such as mass spectrometry-based diagnostics, Raman spectrometry and hyperspectral imaging. Based on our findings, all investigated methods had their advantages and limitations, guiding researchers towards the combined use of intraoperative imaging techniques. This can lead to an improved outcome in terms of extent of tumour resection and progression free survival while preserving neurological outcome of the patients. ispartof: DISCOVER ONCOLOGY vol:13 issue:1 ispartof: location:United States status: published

Radiotherapy (RT) with accelerated beams of charged particles (protons and carbon ions), also known as hadrontherapy, is a treatment modality that is increasingly being adopted thanks to the several benefits that it grants compared to conventional radiotherapy (CRT) treatments performed by means of high-energy photons/electrons. Hence, information about the biomolecular effects in exposed cells caused by such particles is needed to better realize the underlying radiobiological mechanisms and to improve this therapeutic strategy. To this end, Fourier transform infrared microspectroscopy (μ-FT-IR) can be usefully employed, in addition to long-established radiobiological techniques, since it is currently considered a helpful tool for examining radiation-induced cellular changes. In the present study, MCF-10A breast cells were chosen to evaluate the effects of proton exposure using μ-FT-IR. They were exposed to different proton doses and fixed at various times after exposure to evaluate direct effects due to proton exposure and the kinetics of DNA damage repair. Irradiated and control cells were examined in transflection mode using low-e substrates that have been recently demonstrated to offer a fast and direct way to examine proton-exposed cells. The acquired spectra were analyzed using a deconvolution procedure and a ratiometric approach, both of which showed the different contributions of DNA, protein, lipid, and carbohydrate cell components. These changes were particularly significant for cells fixed 48 and 72 h after exposure. Lipid changes were related to variations in membrane fluidity, and evidence of DNA damage was highlighted. The analysis of the Amide III band also indicated changes that could be related to different enzyme contributions in DNA repair.

Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown to depend strongly on the starting feedstock. Five characteristically different graphite sources were exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical examples were compared via a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS and Raman data. A general increase in grafting ratio (ranging from 1.1 wt% up to 25 wt%) and an improvement in grafting stoichiometry (C/R) were observed as flake radius decreased. Raman spectrum imaging of the functionalised natural flake graphite identified that grafting is directed towards flake edges. This behaviour was further corroborated, at atomistic resolution, by functionalising the graphene layers with bipyridine groups able to complex single platinum atoms. The distribution of these groups was then directly imaged using aberration-corrected HAADF-STEM. Platinum atoms were found to be homogeneously distributed across smaller graphenes; in contrast, a more heterogeneous distribution, with a predominance of edge grafting was observed for larger graphites. These observations show that grafting is directed towards flake edges, but not necessary at edge sites; the mechanism is attributed to the relative inaccessibility of the inner basal plane to reactive moieties, resulting in kinetically driven grafting nearer flake edges. This phenomenology may be relevant to a wide range of reactions on graphenes and other 2d materials., The flake size and morphology of the starting material strongly effect the degree and location of grafting when using reductive functionalisation.

Organic functionalization of graphene is successfully performed via 1,3-dipolar cycloaddition of azomethine ylide in the liquid phase. The comparison between 1-methyl-2-pyrrolidinone and N,N-dimethylformamide as dispersant solvents, and between sonication and homogenization as dispersion techniques, proves N,N-dimethylformamide and homogenization as the most effective choice. The functionalization of graphene nanosheets and reduced graphene oxide is confirmed using different techniques. Among them, energy-dispersive X-ray spectroscopy allows to map the pyrrolidine ring of the azomethine ylide on the surface of functionalized graphene, while micro-Raman spectroscopy detects new features arising from the functionalization, which are described in agreement with the power spectrum obtained from ab initio molecular dynamics simulation. Moreover, X-ray photoemission spectroscopy of functionalized graphene allows the quantitative elemental analysis and the estimation of the surface coverage, showing a higher degree of functionalization for reduced graphene oxide. This more reactive behavior originates from the localization of partial charges on its surface due to the presence of oxygen defects, as shown by the simulation of the electrostatic features. Functionalization of graphene using 1,3-dipolar cycloaddition is shown to be a significant step towards the controlled synthesis of graphene-based complex structures and devices at the nanoscale., 15 pages, 8 figures, for associated Supporting Information see http://shorturl.at/dCQ07

The radiation hardness of 180 nm complementary metal–oxide–semiconductor (CMOS) and 55 nm bipolar–CMOS–double-diffused MOS single-photon avalanche diodes (SPADs) is studied using 10 MeV and 100 MeV protons up to a displacement damage dose of 1 PeV/g. It is found that the dark count rate (DCR) levels are dependent on the number and the type of defects created. A new stepwise increase in the DCR is presented. Afterpulsing was found to be a significant contributor to the observed DCR increase. A new model for DCR increase prediction is proposed considering afterpulsing. Most of the samples under test retain reasonable DCR levels after irradiation, showing high tolerance to ionizing and displacement damage caused by protons. Following irradiation, self-healing was observed at room temperature. Furthermore, high-temperature annealing shows potential for accelerating recovery. Overall, the results show the suitability of SPADs as optical detectors for long-term space missions or as detectors for high-energy particles.

Obesity is the main cause of type 2 diabetes mellitus (T2DM). Roux-en-Y gastric bypass (RYGB) surgery is an effective treatment for this obesity-related health problem. However, the adverse effects of T2DM on bone tissue persist or even aggravate after this surgical procedure. As studies on the mandibular condyle bone are scarce, the aim of the present study was to assess its compositional characteristics in T2DM and RYGB conditions. Thirty-two male C57BL/6 mice at 8 weeks of age were randomly assigned to receive either a high-fat or low-fat diet. After 14 weeks of high-fat diet intake, seven obese mice were subjected to RYGB surgery. All animals were euthanized at the age of 30 weeks. Mandibular bones were removed and the trabecular condyle region was assessed using Raman spectroscopy. A decreased mineralization was observed for both T2DM and RYGB condyle bones when compared to controls, with elevated carbonate substitutions for the RYGB group. No compositional differences in crystallinity and presence of advanced glycation end products were found between the groups, with the exception of an increased presence of N-carboxymethyl-lysine in RYGB bone compared to their T2DM counterpart. Site-specific measurements revealed a non-uniform bone composition, with increasing mineralization and carbonate substitutions towards the centre of the mandibular condyle. T2DM and RYGB surgery affect the mandibular condyle bone quality, as investigated at compositional level. Assessment of bone structural properties and remodelling should be carried out to further explore the effects of T2DM and RYGB surgery on this skeleton area. Electronic supplementary material The online version of this article (10.1007/s00223-020-00732-0) contains supplementary material, which is available to authorized users.

The human telomeric G-quadruplex structural motif of DNA has come to be known as a new and stimulating target for anticancer drug discovery. Small molecules that interact with G-quadruplex structures in a selective way have gained impressive interest in recent years as they may serve as potential therapeutic agents. Here, we show how circular dichroism, UV resonance Raman and small angle X-ray scattering spectroscopies can be effectively combined to provide insights into structural and molecular aspects of the interaction between human telomeric quadruplexes and ligands. This study focuses on the ability of berberine and palmatine to bind with human telomeric quadruplexes and provides analysis of the conformational landscape visited by the relevant complexes upon thermal unfolding. With increasing temperature, both free and bound G-quadruplexes undergo melting through a multi-state process, populating different intermediate states. Despite the structural similarity of the two ligands, valuable distinctive features characterising their interaction with the G-quadruplex emerged from our multi-technique approach.

Single-walled carbon nanohorns are an allotrope of carbon with promising properties for a variety of applications. Despite their promise, the majority carrier type (i.e. electrons or holes) that defines the electronic properties of this novel semiconductor is poorly understood and so far only indirect measurements have been employed to arrive at contradictory results. Here, we directly determine the majority carrier type in single-wall carbon nanohorns for the first time by means of thermopower measurements. Using this direct method, we show that SWCNH films exhibit a positive Seebeck coefficient indicating that SWCNHs behave as p-type semiconductors. This result is further corroborated by intentionally tuning the hole or electron concentrations of SWCNH layers via redox doping with molecular electron acceptors and donors, respectively. These results provide a framework for both measuring and chemically tuning the majority carrier type in this emerging nanocarbon semiconductor.

This Review discusses the progresses in label-free nanophotonic biosensors based on photonic or dielectric surfaces and metasurfaces and highlights the challenges and benefits of their applications in the fields of public health, well-being and biosafety., Nanophotonic devices, which control light in subwavelength volumes and enhance light-matter interactions, have opened up exciting prospects for biosensing. Numerous nanophotonic biosensors have emerged to address the limitations of the current bioanalytical methods in terms of sensitivity, throughput, ease-of-use and miniaturization. In this Review, we provide an overview of the recent developments of label-free nanophotonic biosensors using evanescent-field-based sensing with plasmon resonances in metals and Mie resonances in dielectrics. We highlight the prospects of achieving an improved sensor performance and added functionalities by leveraging nanostructures and on-chip and optoelectronic integration, as well as microfluidics, biochemistry and data science toolkits. We also discuss open challenges in nanophotonic biosensing, such as reducing the overall cost and handling of complex biological samples, and provide an outlook for future opportunities to improve these technologies and thereby increase their impact in terms of improving health and safety.

The forensic scenario, on which the round robin study was based, simulated a suspected intentional manipulation of a real estate rental agreement consisting of a total of three pages. The aims of this study were to (i) establish the amount and reliability of information extractable from a single type of evidence and to (ii) provide suggestions on the most suitable combination of compatible techniques for a multi-modal imaging approach to forgery detection. To address these aims, seventeen laboratories from sixteen countries were invited to answer the following tasks questions: (i) which printing technique was used? (ii) were the three pages printed with the same printer? (iii) were the three pages made from the same paper? (iv) were the three pages originally stapled? (v) were the headings and signatures written with the same ink? and (vi) were headings and signatures of the same age on all pages? The methods used were classified into the following categories: Optical spectroscopy, including multispectral imaging, smartphone mapping, UV-luminescence and LIBS ; Infrared spectroscopy, including Raman and FTIR (micro-)spectroscopy ; X-ray spectroscopy, including SEM-EDX, PIXE and XPS ; Mass spectrometry, including ICPMS, SIMS, MALDI and LDIMS ; Electrostatic imaging, as well as non- imaging methods, such as non-multimodal visual inspection, (micro-)spectroscopy, physical testing and thin layer chromatography. The performance of the techniques was evaluated as the proportion of discriminated sample pairs to all possible sample pairs. For the undiscriminated sample pairs, a distinction was made between undecidability and false positive claims. It was found that none of the methods used were able to solve all tasks completely and/or correctly and that certain methods were a priori judged unsuitable by the laboratories for some tasks. Correct results were generally achieved for the discrimination of printer toners, whereas incorrect results in the discrimination of inks. For the discrimination of paper, solid state analytical methods proved to be superior to mass spectrometric methods. None of the participating laboratories deemed addressing ink age feasible. It was concluded that correct forensic statements can only be achieved by the complementary application of different methods and that the classical approach of round robin studies to send standardised subsamples to the participants is not feasible for a true multimodal approach if the techniques are not available at one location.

International audience; In the family of spin-crossover materials, which undergo thermal conversion between low-spin (LS) and high-spin (HS) phases, it is of great interest to study vibrational modes. On the one hand, vibration modes are characteristic of the spin state, and vibrational spectroscopies are often used for monitoring spin-state switching driven by temperature, pressure, or light. On the other hand, spin-state thermal conversion is an entropy-driven process, and the vibrational entropy change represents the main contribution to the total entropy difference between LS and HS phases at solid state. However, the discussion of vibrations in spin-crossover materials is often limited at the molecular scale. Here we study vibration modes in the [Fe(phen)(2)(NCS)(2)] crystal, and we compare symmetry-resolved vibrational spectroscopy data performed on single crystal to density functional theory calculations performed in a periodic three-dimensional crystal. We discuss the complex nature of vibrational modes in crystals, including the vibration of molecules within the crystalline lattice, with different symmetries and frequencies. We also highlight the presence of many low-frequency libration modes of different symmetries. The contribution of vibrational entropy, added to the electronic entropy, provides a total entropy difference in the solid state, which is in very good agreement with calorimetric measurements.

The epithelial barrier hypothesis proposes that the exposure to various epithelial barrier-damaging agents linked to industrialization and urbanization underlies the increase in allergic diseases. The epithelial barrier constitutes the first line of physical, chemical, and immunological defense against environmental factors. Recent reports have shown that industrial products disrupt the epithelial barriers. Innate and adaptive immune responses play an important role in epithelial barrier damage. In addition, recent studies suggest that epithelial barrier dysfunction plays an essential role in the pathogenesis of the atopic march by allergen sensitization through the transcutaneous route. It is evident that external factors interact with the immune system, triggering a cascade of complex reactions that damage the epithelial barrier. Epigenetic and microbiome changes modulate the integrity of the epithelial barrier. Robust and simple measurements of the skin barrier dysfunction at the point-of-care are of significant value as a biomarker, as recently reported using electrical impedance spectroscopy to directly measure barrier defects. Understanding epithelial barrier dysfunction and its mechanism is key to developing novel strategies for the prevention and treatment of allergic diseases. The aim of this review is to summarize recent studies on the pathophysiological mechanisms triggered by environmental factors that contribute to the dysregulation of epithelial barrier function.

In the present work, we elucidate the interplay among energetic bombardment effects in magnetron sputtering and defect generation in two-dimensional (2D) materials. Using deposition of gold (Au) layers on single-layer graphene (SLG) as a model system, we study the effect of pressure-distance (pd) product during magnetron sputtering on the pristine SLG properties. Raman spectroscopy, complemented by X-ray photoelectron spectroscopy, shows that for pd = 8.2 Pa center dot cm, Au layer deposition causes defects in the SLG layer, which gradually diminish and eventually disappear with increasing pd to 82.5 Pa center dot cm. Stochastic and deterministic simulations of the sputtering process, the gas-phase transport, and the interaction of sputtered and plasma species with the substrate surface suggest that defects in SLG primarily emanate from ballistic damage caused by backscattered Ar atoms with energies above 100 eV. With increasing pd, and thereby gas-phase scattering, such high energy Ar species become thermalized and hence incapable of causing atomic displacements in the SLG layer. The overall results of our study suggest that control of backscattered Ar energy is a potential path toward enabling magnetron sputtering for fabrication of multifunctional metal contacts in devices founded upon 2D materials. Funding Agencies|Linkodping University ("LiU Career Contract) [Dnr-LiU-2015-01510]; Swedish research councilSwedish Research CouncilEuropean Commission [VR-2015-04630]; Aforsk foundation [AF 19-137]; Olle Engkvist foundation [SOEB 190-312]; Wenner-Gren foundations [UPD2018-0071, UPD2019-0007]

Stable emissive carbon nanodots were generated in zeolite crystals using near infrared photon irradiation gradually converting the occluded organic template, originally used to synthesize the zeolite crystals, into discrete luminescent species consisting of nano-sized carbogenic fluorophores, as ascertained using Raman microscopy, and steady-state and time-resolved spectroscopic techniques. Photoactivation in a confocal laser fluorescence microscope allows 3D resolved writing of luminescent carbon nanodot patterns inside zeolites providing a cost-effective and non-toxic alternative to previously reported metal-based nanoclusters confined in zeolites, and opens up opportunities in bio-labelling and sensing applications. ispartof: Chemical Communications vol:57 issue:90 pages:11952-11955 ispartof: location:England status: published

Screen-printed carbon electrodes (SPCEs) are enjoying increasing popularity in different electrochemistry areas, from electroanalysis to energy storage and power generation. Highly oriented pyrolytic graphite (HOPG), an ordered form of graphite, displays excellent electrochemical properties. However, its application in screen-printed electrodes has remained elusive. In this work, we present a straightforward laser-based process to selectively transform, in ambient conditions, the surface of conventional SPCEs into highly homogeneous HOPG. Energy densities between 6.8 and 7.7 mJ cm(-2) result in a binder-free, high-purity HOPG surface with very fast electron transfer rates. The electrode transformation to HOPG has been followed by SEM, Raman spectroscopy and XPS. Cyclic voltammetry of model systems ferrocyanide, ferrocenecarboxylic acid, dopamine and hydroquinone has been used to determine variations in electrode kinetics (from 50% increase for ferrocenecarboxylic acid, up to ca. 2 orders of magnitude for ferrocyanide and dopamine) and interfacial capacitance (from 40 up to 220 mu F cm(-2)). Finally, differential pulse voltammetry (DPV) has been used to demonstrate the ability of these electrodes to detect dopamine in the presence of an excess amount of ascorbic acid. The authors are grateful for the technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). We acknowledge funding from the European Union's Horizon 2020 Programme for Research, ICT-02-2018 - Flexible and Wearable Electronics, Grant agreement no. 825339 - WEARPLEX. Lia Campos-Arias thanks the University of Basque Country (UPV/EHU) for doctoral grant PIFI20/04. Project number PID2020-113154RB-C22 from the Spanish Ministry of Science and Innovation is also gratefully acknowledged.

The diagnosis is the art of determining the nature of a disease, and an accurate diagnosis is the true cornerstone on which rational treatment should be built. Within the workflow in the management of head and neck tumours, there are different types of diagnosis. The purpose of this work is to point out the differences and the aims of the different types of diagnoses and to highlight their importance in the management of patients with head and neck tumours. Qualitative diagnosis is performed by a pathologist and is essential in determining the management and can provide guidance on prognosis. The evolution of immunohistochemistry and molecular biology techniques has made it possible to obtain more precise diagnoses and to identify prognostic markers and precision factors. Quantitative diagnosis is made by the radiologist and consists of identifying a mass lesion and the estimation of the tumour volume and extent using imaging techniques, such as CT, MRI, and PET. The distinction between the two types of diagnosis is clear, as the methodology is different. The accurate establishment of both diagnoses plays an essential role in treatment planning. Getting the right diagnosis is a key aspect of health care, and it provides an explanation of a patient's health problem and informs subsequent decision. Deep learning and radiomics approaches hold promise for improving diagnosis.

Answering the question of whether life ever existed on Mars is a key goal of both NASA's and ESA's imminent Mars rover missions. The obfuscatory effects of oxidizing salts, such as perchlorates and sulfates, on organic matter during thermal decomposition analysis techniques are well established. Less well studied are the transformative effects of iron oxides and (oxy)hydroxides, which are present in great abundances in the martian regolith. We examined the products of flash pyrolysis-gas chromatography-mass spectrometry (a technique analogous to the thermal techniques employed by past, current, and future landed Mars missions) which form when the cyanobacteria Arthrospira platensis are heated in the presence of a variety of Mars-relevant iron-bearing minerals. We found that iron oxides/(oxy)hydroxides have transformative effects on the pyrolytic products of cyanobacterial biomolecules. Both the abundance and variety of molecular species detected were decreased as iron substrates transformed biomolecules, by both oxidative and reductive processes, into lower fidelity alkanes, aromatic and aryl-bonded hydrocarbons. Despite the loss of fidelity, a suite that contains mid-length alkanes and polyaromatic hydrocarbons and/or aryl-bonded molecules in iron-rich samples subjected to pyrolysis may allude to the transformation of cyanobacterially derived mid-long chain length fatty acids (particularly unsaturated fatty acids) originally present in the sample. Hematite was found to be the iron oxide with the lowest transformation potential, and because this iron oxide has a high affinity for codeposition of organic matter and preservation over geological timescales, sampling at Mars should target sediments/strata that have undergone a diagenetic history encouraging the dehydration, dihydroxylation, and oxidation of more reactive iron-bearing phases to hematite by looking for (mineralogical) evidence of the activity of oxidizing, acidic/neutral, and either hot or long-lived fluids.

In clinical settings, the dosing and differential diagnosis of the poisoning of morphine (MO) and codeine (CO) is challenging due to interindividual variations in metabolism. However, direct electrochemical detection of these analytes from biological matrices is inherently challenging due to interference from large concentrations of anions, such as ascorbic acid (AA) and uric acid (UA), as well as fouling of the electrode by proteins. In this work, a disposable Nafion-coated single-walled carbon nanotube network (SWCNT) electrode was developed. We show facile electron transfer and efficient charge separation between the interfering anions and positively charged MO and CO, as well as significantly reduced matrix effect in human plasma. The Nafion coating alters the voltammetric response of MO and CO, enabling simultaneous detection. With this SWCNT/Nafion electrode, two linear ranges of 0.05-1 and 1-10 mu M were found for MO and one linear range of 0.1-50 mu M for CO. Moreover, the selective and simultaneous detection of MO and CO was achieved in large excess of AA and UA, as well as, for the first time, in unprocessed human plasma. The favorable properties of this electrode enabled measurements in plasma with only mild dilution and without the precipitation of proteins.

In this paper, the effect of the gaseous environment on recrystallization of amorphous paracetamol was investigated. The experiments were conducted with a headspace gas consisting of dry air, dry carbon dioxide, dry nitrogen and humid air in four temperatures ranging from 5 degrees C below onset of T-g to 5 degrees C above onset of T-g. The recrystallization was monitored using Raman spectroscopy and subsequent multivariate analysis. In temperatures below onset of T-g, the presence of oxygen delayed the onset of recrystallization, with an increasing delay with lower temperature. When comparing samples exposed to dry headspace gases, the crystallization was fastest below onset of Tg when exposed to nitrogen. Being an inert gas, nitrogen did not seem to interfere with the molecules allowing them to freely find their inherent arrangement, whereas the presence of oxygen delayed the formation of stabile nuclei. Above onset of T-g, no differences in onset of crystallization was detected between dry gas atmospheres. Amorphous paracetamol crystallized to form II in all measurements and the samples did not reach full crystallinity within the duration of the experiments. The results show that the headspace gas has an effect on nucleation in the amorphous sample.

Additive manufacturing (3D printing) is a disruptive technology that is changing production systems globally. In addition, microfluidic devices are increasingly being used for chemical analysis and continuous production of chemicals. Printing of materials such as polymers and metals is already a reality, but additive manufacturing of glass for microfluidic systems has received minor attention. We characterize microfluidic devices (channel cross-section dimensions down to a scale of 100 mm) that have been produced by additive manufacturing of molten soda-lime glass in tens of minutes and report their mass spectrometric and Raman spectroscopic analysis examples. The functionality of a microfluidic glass microreactor is shown with online mass spectrometric analysis of linezolid synthesis. Additionally, the performance of a direct infusion device is demonstrated by mass spectrometric analysis of drugs. Finally, the excellent optical quality of the glass structures is demonstrated with in-line Raman spectroscopic measurements. Our results promise a bright future for additively manufactured glass microdevices in diverse fields of science.

Hydrogels are a popular class of biomaterial that are used in a number of commercial applications (e.g.; contact lenses, drug delivery, and prophylactics). Alginate-based tough hydrogel systems, interpenetrated with acrylamide, reportedly form both ionic and covalent cross-links, giving rise to their remarkable mechanical properties. In this work, we explore the nature, onset and extent of such hybrid bonding interactions between the complementary networks in a model double-network alginate-acrylamide system, using a host of characterisation techniques (e.g.; FTIR, Raman, UV-vis, and fluorescence spectroscopies), in a time-resolved manner. Further, due to the similarity of bonding effects across many such complementary, interpenetrating hydrogel networks, the broad bonding interactions and mechanisms observed during gelation in this model system, are thought to be commonly replicated across alginate-based and broader double-network hydrogels, where both physical and chemical bonding effects are present. Analytical techniques followed real-time bond formation, environmental changes and re-organisational processes that occurred. Experiments broadly identified two phases of reaction; phase I where covalent interaction and physical entanglements predominate, and; phase II where ionic cross-linking effects are dominant. Contrary to past reports, ionic cross-linking occurred more favourably via mannuronate blocks of the alginate chain, initially. Evolution of such bonding interactions was also correlated with the developing tensile and compressive properties. These structure-property findings provide mechanistic insights and future synthetic intervention routes to manipulate the chemo-physico-mechanical properties of dynamically-forming tough hydrogel structures according to need (i.e.; durability, biocompatibility, adhesion, etc.), allowing expansion to a broader range of more physically and/or environmentally demanding biomaterials applications. ispartof: RSC ADVANCES vol:11 issue:18 pages:10710-10726 ispartof: location:England status: published

The integration of real time release testing into an advanced process control (APC) concept in combination with digital twins accelerates the process towards autonomous operation. In order to implement this, on the one hand, measurement technology is required that is capable of measuring relevant process data online, and on the other hand, a suitable model must be available to calculate new process parameters from this data, which are then used for process control. Therefore, the feasibility of online measurement techniques including Raman-spectroscopy, attenuated total reflection Fourier transformed infrared spectroscopy (ATR-FTIR), diode array detector (DAD) and fluorescence is demonstrated within the framework of the process analytical technology (PAT) initiative. The best result is achieved by Raman, which reliably detected mAb concentration (R2 of 0.93) and purity (R2 of 0.85) in real time, followed by DAD. Furthermore, the combination of DAD and Raman has been investigated, which provides a promising extension due to the orthogonal measurement methods and higher process robustness. The combination led to a prediction for concentration with a R2 of 0.90 ± 3.9% and for purity of 0.72 ± 4.9%. These data are used to run simulation studies to show the feasibility of process control with a suitable digital twin within the APC concept.