Simulations of charge transport in organic compounds

To aid the design of organic semiconductors, we study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The results are compared for the different compounds and methods and, where available, with experimental data. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. When taking only intra-columnar transport into account, the mobility is orders of magnitude lower than in the three-dimensional case. BTBT is a promising material for solution-processed organic field-effect transistors. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The resulting broad transfer integral distributions modify the connectivity of the system but sufficiently many fast percolation paths remain for the charges. Rubrene, indolocarbazole and BBBT are examples of crystals without significant static disorder. The high mobility of rubrene is explained by two main features: first, the shifted cofacial alignment of its molecules, and second, the high center of mass vibrational frequency. In comparsion to SCD, only KMC based on Marcus rates is capable of describing neighbors with low coupling and of taking static disorder into account three-dimensionally. Thus it is the method of choice for crystalline systems dominated by static disorder. However, it is inappropriate for the case of strong coupling and underestimates the mobility of well-ordered crystals. SCD, despite its one-dimensionality, is valuable for crystals with strong coupling and little disorder. It also allows correct treatment of dynamical effects, such as intermolecular vibrations of the molecules. Rate equations are incapable of this, because simulations are performed on static snapshots. We have thus shown strengths and weaknesses of two state of the art models used to study charge transport in organic compounds, partially developed a program to compute and visualize transfer integral distributions and other charge transport properties, and found structure-mobility relations for several promising organic semiconductors.

Comparison of affinity chromatography supports for separation of protein

Chromatography is the most widely used technique for high-resolution separation and analysis of proteins. This technique is very useful for the purification of delicate compounds, e.g. pharmaceuticals, because it is usually performed at milder conditions than separation processes typically used by chemical industry. This thesis focuses on affinity chromatography. Chromatographic processes are traditionally performed using columns packed with porous resin. However, these supports have several limitations, including the dependence on intra-particle diffusion, a slow mass transfer mechanism, for the transport of solute molecules to the binding sites within the pores and high pressure drop through the packed bed. These limitations can be overcome by using chromatographic supports like membranes or monoliths. Dye-ligands are considered important alternatives to natural ligands. Several reactive dyes, particularly Cibacron Blue F3GA, are used as affinity ligand for protein purification. Cibacron Blue F3GA is a triazine dye that interacts specifically and reversibly with albumin. The aim of this study is to prepare dye-affinity membranes and monoliths for efficient removal of albumin and to compare the three different affinity supports: membranes and monoliths and a commercial column HiTrapTM Blue HP, produced by GE Healthcare. A comparison among the three supports was performed in terms of binding capacity at saturation (DBC100%) and dynamic binding capacity at 10% breakthrough (DBC10%) using solutions of pure BSA. The results obtained show that the CB-RC membranes and CB-Epoxy monoliths can be compared to commercial support, column HiTrapTM Blue HP, for the separation of albumin. These results encourage a further characterization of the new supports examined.

High gradient magnetic separation (HGMS) of erythrocytes infected with plasmodium falciparum

This thesis was undertaken to explore possible applications of high gradient magnetic separation (HGMS) for the separation of RBCs infected with Plasmodium falciparum, with the dual aim of establishing a novel and superior method for isolating late-stage infected cells, and of obtaining synchronized cell cultures.rnThe presented work presents protocols for HGMS of parasitized RBCs that fulfil these aims. Late-stage parasitized cell can be isolated essentially devoid of contamination with non-infected and ring-stage infected cells. Such an easy method for a highly quantitative and qualitative purification has not yet been reported. Synchronous cultures can be obtained both following depletion of late-stage infected cells, and following isolation of the latter. The quality of synchronization cultures matches that of sorbitol lysis, the current standard method for malaria culture synchronization. An advantage of HGMS is the avoidance of osmotic stress for RBCs. The new methods further have the appeal of high reproducibility, cost-effectiveness, and simple protocol.rnIt should be possible to take the methods beyond Plasmodium infected RBCs. Most magnetic separation techniques in the sector of biomedical research employ columns with a hydrophilic polymer-coated matrix. Our procedure employs an optimized buffer system. Polymer coating becomes unnecessary and uncoated columns are available at a fraction of the cost.

Neural network activity in the neonatal rat barrel cortex in vivo

Coordinated patterns of electrical activity are important for the early development of sensory systems. The spatiotemporal dynamics of these early activity patterns and the role of the peripheral sensory input for their generation are essentially unknown. There are two projects in this thesis. In project1, we performed extracellular multielectrode recordings in the somatosensory cortex of postnatal day 0 to 7 rats in vivo and observed three distinct patterns of synchronized oscillatory activity. (1) Spontaneous and periphery-driven spindle bursts of 1–2 s in duration and ~10 Hz in frequency occurred approximately every 10 s. (2) Spontaneous and sensory-driven gamma oscillations of 150–300 ms duration and 30–40 Hz in frequency occurred every 10–30 s. (3) Long oscillations appeared only every ~20 min and revealed the largest amplitude (250–750 µV) and longest duration (>40 s). These three distinct patterns of early oscillatory activity differently synchronized the neonatal cortical network. Whereas spindle bursts and gamma oscillations did not propagate and synchronized a local neuronal network of 200–400 µm in diameter, long oscillations propagated with 25–30 µm/s and synchronized 600-800 µm large ensembles. All three activity patterns were triggered by sensory activation. Single electrical stimulation of the whisker pad or tactile whisker activation elicited neocortical spindle bursts and gamma activity. Long oscillations could be only evoked by repetitive sensory stimulation. The neonatal oscillatory patterns in vivo depended on NMDAreceptor-mediated synaptic transmission and gap junctional coupling. Whereas spindle bursts and gamma oscillations may represent an early functional columnar-like pattern, long oscillations may serve as a propagating activation signal consolidating these immature neuronal networks. In project2, Using voltage-sensitive dye imaging and simultaneous multi-channel extracellular recordings in the barrel cortex and somatosensory thalamus of newborn rats in vivo, we found that spontaneous and whisker stimulation induced activity patterns were restricted to functional cortical columns already at the day of birth. Spontaneous and stimulus evoked cortical activity consisted of gamma oscillations followed by spindle bursts. Spontaneous events were mainly generated in the thalamus or by spontaneous whisker movements. Our findings indicate that during early developmental stages cortical networks self-organize in ontogenetic columns via spontaneous gamma oscillations triggered by the thalamus or sensory periphery.

Experimental assessment of environmental decay effects in masonry via non destructive diagnostic techniques and mechanical tests

Environmental decay in porous masonry materials, such as brick and mortar, is a widespread problem concerning both new and historic masonry structures. The decay mechanisms are quite complex dependng upon several interconnected parameters and from the interaction with the specific micro-climate. Materials undergo aesthetical and substantial changes in character but while many studies have been carried out, the mechanical aspect has been largely understudied while it bears true importance from the structural viewpoint. A quantitative assessment of the masonry material degradation and how it affects the load-bearing capacity of masonry structures appears missing. The research work carried out, limiting the attention to brick masonry addresses this issue through an experimental laboratory approach via different integrated testing procedures, both non-destructive and mechanical, together with monitoring methods. Attention was focused on transport of moisture and salts and on the damaging effects caused by the crystallization of two different salts, sodium chloride and sodium sulphate. Many series of masonry specimens, very different in size and purposes were used to track the damage process since its beginning and to monitor its evolution over a number of years Athe same time suitable testing techniques, non-destructive, mini-invasive, analytical, of monitoring, were validated for these purposes. The specimens were exposed to different aggressive agents (in terms of type of salt, of brine concentration, of artificial vs. open-air natural ageing, …), tested by different means (qualitative vs. quantitative, non destructive vs. mechanical testing, punctual vs. wide areas, …), and had different size (1-, 2-, 3-header thick walls, full-scale walls vs. small size specimens, brick columns and triplets vs. small walls, masonry specimens vs. single units of brick and mortar prisms, …). Different advanced testing methods and novel monitoring techniques were applied in an integrated holistic approach, for quantitative assessment of masonry health state.

Ricostruzione della colonna anteriore dopo resezione tumorale: Utilizzo di gabbia in titanio/carbonio o innesto osseo allogenico armato in titanio?

Il rachide è stato suddiviso in tre colonne da Denis: anteriore e centrale comprendono la metà anteriore del corpo vertebrale, la metà posteriore e l’inizio dei peduncoli, mentre la colonna posteriore comprende l’arco e i peduncoli stessi. In caso di resezione o lesione della colonna anteriore e media è indicata la ricostruzione. Diverse tecniche e materiali possono essere usati per ricostruire il corpo vertebrale. Innesti vascolarizzati, autograft, allograft sono stati usati, così come impianti sintetici di titanio o materiale plastico come il PEEK (Poly etere etere ketone). Tutti questi materiali hanno vantaggi e svantaggi in termini di proprietà intrinseche, resistenza meccanica, modulo di elasticità, possibilità di trasmissione malattie, capacità di fondersi con l’osso ospite o meno. Le soluzioni più usate sono le cage in titanio o carbonio, il PMMA ( Poli methil metacrilato), gli innesti ossei massivi. Si è effettuato uno studio di coorte retrospettivo paragonando due gruppi di pazienti oncologici spinali trattati da due chirurghi esperti in un centro di riferimento, con vertebrectomia e ricostruzione della colonna anteriore: un gruppo con cage in carbonio o titanio, l’altro gruppo con allograft massivo armato di innesto autoplastico o mesh in titanio. Si sono confrontati i risultati in termini di cifosi segmenterai evolutiva, fusione ossea e qualità di vita del paziente. Il gruppo delle cage in carbonio / titanio ha avuto risultati leggermente migliori dal punto di vista biomeccanico ma non statisticamente significativo, mentre dal punto di vista della qualità di vita i risultati sono stati migliori nel gruppo allograft. Non ci sono stati fallimenti meccanici della colonna anteriore in entrambi i gruppi, con un Fu tra 12 e 60 mesi. Si sono paragonati anche i costi delle due tecniche. In conclusione l’allogar è una tecnica sicura ed efficace, con proprietà meccaniche solide, soprattutto se armato con autograft o mesi in titanio.

Città e architettura a Faenza nel Rinascimento. Progetti e strategie di rinnovamento urbano nell'età di Carlo II Manfredi (1468-77)

La tesi ha come oggetto il rinnovamento urbano che fu realizzato a Faenza per opera del suo signore Carlo II Manfredi tra il 1468 e il 1477, d’accordo con il fratello, il vescovo Federico. La prima opera realizzata da Carlo fu il portico a due livelli che dotò di una nuova facciata il suo palazzo di residenza, di origini medievali. Questa architettura sarebbe stata il preludio di un riordino generale della piazza principale della città, probabilmente allo scopo di ricreare un foro all’antica, come prescritto dai trattati di Vitruvio e di Alberti. L’aspetto originale del loggiato rinascimentale, desumibile da documentazione archivistica e iconografica, permette di attribuirlo con una certa probabilità a Giuliano da Maiano. Oltre alla piazza, Carlo riformò profondamente il tessuto urbano, demolendo molti portici lignei di origine medievale, rettificando le principali strade, completando la cerchia muraria. Federico Manfredi nel 1474 diede inizio alla fabbrica della Cattedrale, ricostruita dalle fondamenta su progetto dello stesso Giuliano da Maiano. L’architettura della chiesa ha uno stile largamente debitore all’architettura sacra di Brunelleschi, ma con significative differenze (come la navata definita da un’alternanza tra pilastri e colonne, o la copertura composta da volte a vela). L’abside della cattedrale, estranea al progetto maianesco, fu realizzata nel 1491-92 e mostra alcuni dettagli riconducibili alla coeva architettura di Bramante. A Faenza si realizza in un periodo di tempo brevissimo una profonda trasformazione del volto della città: loggiato, riforma della piazza, riordino delle strade, una nuova cattedrale, tutto contribuisce a dare lustro ai Manfredi e a fare di Faenza una città moderna e in cui si mettono in pratica, forse per la prima volta nell’Italia settentrionale, i dettami di Vitruvio e di Alberti.

On arc-routing problems

Das Basisproblem von Arc-Routing Problemen mit mehreren Fahrzeugen ist das Capacitated Arc-Routing Problem (CARP). Praktische Anwendungen des CARP sind z.B. in den Bereichen Müllabfuhr und Briefzustellung zu finden. Das Ziel ist es, einen kostenminimalen Tourenplan zu berechnen, bei dem alle erforderlichen Kanten bedient werden und gleichzeitig die Fahrzeugkapazität eingehalten wird. In der vorliegenden Arbeit wird ein Cut-First Branch-and-Price Second Verfahren entwickelt. In der ersten Phase werden Schnittebenen generiert, die dem Master Problem in der zweiten Phase hinzugefügt werden. Das Subproblem ist ein kürzeste Wege Problem mit Ressourcen und wird gelöst um neue Spalten für das Master Problem zu liefern. Ganzzahlige CARP Lösungen werden durch ein neues hierarchisches Branching-Schema garantiert. Umfassende Rechenstudien zeigen die Effektivität dieses Algorithmus. Kombinierte Standort- und Arc-Routing Probleme ermöglichen eine realistischere Modellierung von Zustellvarianten bei der Briefzustellung. In dieser Arbeit werden jeweils zwei mathematische Modelle für Park and Loop und Park and Loop with Curbline vorgestellt. Die Modelle für das jeweilige Problem unterscheiden sich darin, wie zulässige Transfer Routen modelliert werden. Während der erste Modelltyp Subtour-Eliminationsbedingungen verwendet, werden bei dem zweiten Modelltyp Flussvariablen und Flusserhaltungsbedingungen eingesetzt. Die Rechenstudie zeigt, dass ein MIP-Solver den zweiten Modelltyp oft in kürzerer Rechenzeit lösen kann oder bei Erreichen des Zeitlimits bessere Zielfunktionswerte liefert.

The analysis of the collapse of a precast r.c. industrial building during the 29th may 2012 emilia romagna earthquake

Analysis of the collapse of a precast r.c. industrial building during the 2012 Emilia earthquake, focus on the failure mechanisms in particular on the flexure-shear interactions. Analysis performed by a time history analysis using a FEM model with the software SAP2000. Finally a reconstruction of the collapse on the basis of the numerical data coming from the strength capacity of the elements failed, using formulation for lightly reinforced columns with high shear and bending moment.

The influence of infill walls on seismic behavior of a historical building in Shanghai

Seismic assessment and seismic strengthening are the key issues need to be figured out during the process of protection and reusing of historical buildings. In this thesis the seismic behaviors of the hinged steel structure, a typical structure of historical buildings, i.e. hinged steel frames in Shanghai, China, were studied based on experimental investigations and theoretic analysis. How the non-structural members worked with the steel frames was analyzed thoroughly. Firstly, two 1/4 scale hinged steel frames were constructed based on the structural system of Bund 18, a historical building in Shanghai: M1 model without infill walls, M2 model with infill walls, and tested under the horizontal cyclic loads to investigate their seismic behavior. The Shaking Table Test and its results indicated that the seismic behavior of the hinged steel frames could be improved significantly with the help of non-structural members, i.e., surrounding elements outside the hinged steel frames and infilled walls. To specify, the columns are covered with bricks, they consist of I shape formed steel sections and steel plates, which are clenched together. The steel beams are connected to the steel column by steel angle, thus the structure should be considered as a hinged frame. And the infilled wall acted as a compression diagonal strut to withstand the horizontal load, therefore, the seismic capacity and stiffness of the hinged steel frames with infilled walls could be estimated by using the equivalent compression diagonal strut model. A SAP model has been constructed with the objective to perform a dynamic nonlinear analysis. The obtained results were compared with the results obtained from Shaking Table Test. The Test Results have validated that the influence of infill walls on seismic behavior can be estimated by using the equivalent diagonal strut model.

Multicentre validation study of nucleic acids extraction from FFPE tissues

In most pathology laboratories worldwide, formalin-fixed paraffin embedded (FFPE) samples are the only tissue specimens available for routine diagnostics. Although commercial kits for diagnostic molecular pathology testing are becoming available, most of the current diagnostic tests are laboratory-based assays. Thus, there is a need for standardized procedures in molecular pathology, starting from the extraction of nucleic acids. To evaluate the current methods for extracting nucleic acids from FFPE tissues, 13 European laboratories, participating to the European FP6 program IMPACTS (www.impactsnetwork.eu), isolated nucleic acids from four diagnostic FFPE tissues using their routine methods, followed by quality assessment. The DNA-extraction protocols ranged from homemade protocols to commercial kits. Except for one homemade protocol, the majority gave comparable results in terms of the quality of the extracted DNA measured by the ability to amplify differently sized control gene fragments by PCR. For array-applications or tests that require an accurately determined DNA-input, we recommend using silica based adsorption columns for DNA recovery. For RNA extractions, the best results were obtained using chromatography column based commercial kits, which resulted in the highest quantity and best assayable RNA. Quality testing using RT-PCR gave successful amplification of 200 bp-250 bp PCR products from most tested tissues. Modifications of the proteinase-K digestion time led to better results, even when commercial kits were applied. The results of the study emphasize the need for quality control of the nucleic acid extracts with standardised methods to prevent false negative results and to allow data comparison among different diagnostic laboratories.

Intermittent spike-wave dynamics in a heterogeneous, spatially extended neural mass model

Generalised epileptic seizures are frequently accompanied by sudden, reversible transitions from low amplitude, irregular background activity to high amplitude, regular spike-wave discharges (SWD) in the EEG. The underlying mechanisms responsible for SWD generation and for the apparently spontaneous transitions to SWD and back again are still not fully understood. Specifically, the role of spatial cortico-cortical interactions in ictogenesis is not well studied. We present a macroscopic, neural mass model of a cortical column which includes two distinct time scales of inhibition. This model can produce both an oscillatory background and a pathological SWD rhythm. We demonstrate that coupling two of these cortical columns can lead to a bistability between out-of-phase, low amplitude background dynamics and in-phase, high amplitude SWD activity. Stimuli can cause state-dependent transitions from background into SWD. In an extended local area of cortex, spatial heterogeneities in a model parameter can lead to spontaneous reversible transitions from a desynchronised background to synchronous SWD due to intermittency. The deterministic model is therefore capable of producing absence seizure-like events without any time dependent adjustment of model parameters. The emergence of such mechanisms due to spatial coupling demonstrates the importance of spatial interactions in modelling ictal dynamics, and in the study of ictogenesis.

Molybdenum isotope fractionation in pelagic euxinia: Evidence from the modern Black and Baltic Seas

Here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the Black Sea and two deeps of the Baltic Sea. Dissolved molybdenum in all water samples is depleted in salinity-normalized concentration and enriched in the heavy isotope (δ98Mo values up to + 2.9‰) compared to previously published isotope data of sedimentary molybdenum from the same range of water depths. Furthermore, δ98Mo values of all water samples from the Black Sea and anoxic deeps of the Baltic Sea are heavier than open ocean water. The observed isotope fractionation between sediments and the anoxic water column of the Black Sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions. An extrapolation to a theoretical pure MoS42− solution indicates a fractionation constant between MoS42− and authigenic solid Mo of 0.5 ± 0.3‰. Measured waters with all thiomolybdates coexisting in various proportions show larger but non-linear fractionation. The best explanation for our field observations is Mo scavenging by the thiomolybdates, dominantly — but not exclusively — present in the form of MoS42−. The Mo isotopic compositions of samples from the sediments and anoxic water column of the Baltic Sea are in overall agreement with those of the Black Sea at intermediate depth and corresponding sulphide concentrations. The more dynamic changes of redox conditions in the Baltic deeps complicate the Black Sea-derived relationship between thiomolybdates and Mo isotopic composition. In particular, the occasional flushing/mixing, of the deep waters, affects the corresponding water column and sedimentary data. δ98Mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations. The results can be explained by non-conservative behaviour of Mo under suboxic to anoxic conditions in the shallow bottom parts of the basin, most pronounced on the NW shelf of the Black Sea.

Proteomic and peptidomic study of proteolysis in quarter milk after infusion with lipoteichoic acid from Staphylococcus aureus

Mastitic milk is associated with increased bovine protease activity, such as that from plasmin and somatic cell enzymes, which cause proteolysis of the caseins and may reduce cheese yield and quality. The aim of this work was to characterize the peptide profile resulting from proteolysis in a model mastitis system and to identify the proteases responsible. One quarter of each of 2 cows (A and B) was infused with lipoteichoic acid from Staphylococcus aureus. The somatic cell counts of the infused quarters reached a peak 6h after infusion, whereas plasmin activity of those quarters also increased, reaching a peak after 48 and 12h for cow A and B, respectively. Urea-polyacrylamide gel electrophoretograms of milk samples of cow A and B obtained at different time points after infusion and incubated for up to 7 d showed almost full hydrolysis of beta- and alpha(S1)-casein during incubation of milk samples at peak somatic cell counts, with that of beta-casein being faster than that of alpha(S1)-casein. Two-dimensional gel electrophoretograms of milk 6h after infusion with the toxin confirmed hydrolysis of beta- and alpha(S1)-casein and the appearance of lower-molecular-weight products. Peptides were subsequently separated by reversed-phase HPLC and handmade nanoscale C(18) columns, and identified by matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry. Twenty different peptides were identified and shown to originate from alpha(s1)- and beta-casein. Plasmin, cathepsin B and D, elastase, and amino- and carboxypeptidases were suggested as possible responsible proteases based on the peptide cleavage sites. The presumptive activity of amino- and carboxypeptidases is surprising and may indicate the activity of cathepsin H, which has not been reported in milk previously.

CH4, CO, and H2O spectroscopy for the Sentinel-5 Precursor mission: an assessment with the Total Carbon Column Observing Network measurements

The TROPOspheric Monitoring Instrument (TROPOMI) will be part of ESA's Sentinel-5 Precursor (S5P) satellite platform scheduled for launch in 2015. TROPOMI will monitor methane and carbon monoxide concentrations in the Earth's atmosphere by measuring spectra of back-scattered sunlight in the short-wave infrared (SWIR). S5P will be the first satellite mission to rely uniquely on the spectral window at 4190–4340 cm−1 (2.3 μm) to retrieve CH4 and CO. In this study, we investigated if the absorption features of the three relevant molecules CH4, CO, and H2O are adequately known. To this end, we retrieved total columns of CH4, CO, and H2O from absorption spectra measured by two ground-based Fourier transform spectrometers that are part of the Total Carbon Column Observing Network (TCCON). The retrieval results from the 4190–4340 cm−1 range at the TROPOMI resolution (0.45 cm−1) were then compared to the CH4 results obtained from the 6000 cm−1 region, and the CO results obtained from the 4190–4340 cm−1 region at the higher TCCON resolution (0.02 cm−1). For TROPOMI-like settings, we were able to reproduce the CH4 columns to an accuracy of 0.3% apart from a constant bias of 1%. The CO retrieval accuracy was, through interference, systematically influenced by the shortcomings of the CH4 and H2O spectroscopy. In contrast to CH4, the CO column error also varied significantly with atmospheric H2O content. Unaddressed, this would introduce seasonal and latitudinal biases to the CO columns retrieved from TROPOMI measurements. We therefore recommend further effort from the spectroscopic community to be directed at the H2O and CH4 spectroscopy in the 4190–4340 cm−1 region.