The Structural Characterisation and DFT-Aided Interpretation of Vibrational Spectra for Cyclo(l-Cys-d-Cys) Cyclic Dipeptide in a Solid State.

Cyclic dipeptides with two intramolecular peptide bonds forming a six-membered 2,5-diketopiperazine ring are gaining significant attention due to their biological and chemical properties. Small changes in the local geometry of such molecules (from cis to trans) can lead to significant structural differences. This work presents the results of a study of cyclo(l-Cys-d-Cys), a dipeptide comprising two cysteine molecules in opposite chiral configurations, with the functional groups situated at both sides of the diketopiperazine ring. X-ray diffraction (XRD) experiment revealed that the molecule crystallises in the P-1 space group, which includes the centre of inversion. The IR and Raman vibrational spectra of the molecule were acquired and interpreted in terms of the potential energy distribution (PED) according to the results of density functional theory (DFT) calculations. The DFT-assisted analysis of energy frameworks for the hydrogen bond network within molecular crystals was performed to support the interpretation of X-ray structural data. The optimisation of the computational model based on three-molecule geometry sections from the crystallographic structure, selected to appropriately reflect the intermolecular interactions responsible for the formation of 1D molecular tapes in cyclo(l-Cys-d-Cys) crystal, allowed for better correspondence between theoretical and experimental vibrational spectra. This work can be considered the first complete structural characterisation of cyclo(l-Cys-d-Cys), complemented via vibrational spectroscopy results with full band assignment aided with the use of the DFT method.

Reduced Self-Aggregation and Improved Stability of Silica-Coated Fe3O4/Ag SERS-Active Nanotags Functionalized With 2-Mercaptoethanesulfonate.

Nanocomposites combining magnetic and plasmonic properties are very attractive within the field of surface-enhanced Raman scattering (SERS) spectroscopy. Applications presented so far take advantage of not only the cooperation of both components but also synergy (enhanced properties), leading to multi-approach analysis. While many methods were proposed to synthesize such plasmonic-magnetic nanoparticles, the issue of their collective magnetic behavior, inducing irreversible self-aggregation, has not been addressed yet. Thus, here we present a simple and fast method to overcome this problem, employing 2-mercaptoethanesulfonate (MES) ions as both a SERS tag and primer molecules in the silica-coating process of the previously fabricated Fe3O4/Ag nanocomposite. The use of MES favored the formation of silica-coated nanomaterial comprised of well-dispersed small clusters of Fe3O4/Ag nanoparticles. Furthermore, adsorbed MES molecules provided a reliable SERS response, which was successfully detected after magnetic assembly of the Fe3O4/Ag@MES@SiO2 on the surface of the banknote. Improved chemical stability after coating with a silica layer was also found when the nanocomposite was exposed to suspension of yeast cells. This work reports on the application of 2-mercaptoethanesulfonate not only providing a photostable SERS signal due to a non-aromatic Raman reporter but also acting as a silica-coating primer and a factor responsible for a substantial reduction of the self-aggregation of the plasmonic-magnetic nanocomposite. Additionally, here obtained Fe3O4/Ag@MES@SiO2 SERS nanotags showed the potential as security labels for the authentication purposes, retaining its original SERS performance after deposition on the banknote.

Reduced graphene oxide doping with nanometer-sized ferrocene moieties - New active material for glucose redox sensors.

Herein, we present that the reduced graphene oxide (rGO) doped with nanometer-sized ferrocene moieties is a new, excellent active material for redox sensors. Two distinct approaches were utilized for the modification of rGO. The first method was based on the covalent decoration of rGO via the addition of azomethine ylide generated from the ferrocenecarboxaldehyde oxime. The second approach utilized the adsorption of 1,1'-ferrocenedicarboxylic acid on the graphene sheet via the π-π stacking. The morphology of the synthesized graphene materials was studied by application of microscopic techniques, whereas the Raman data allowed the characteristics of the tested materials in terms of their structural properties. The tested graphene materials doped with ferrocene moieties were used as a bioactive platform for glucose oxidase (GOx) immobilization. The enzyme was immobilized onto the rGO materials in two ways: (i) using a crosslinking agent - glutaraldehyde (GA) and (ii) by formation of the amide bonds between carboxylic groups of rGO-Fc(COOH)2 and amine groups from enzyme. Ferrocene moieties present at the graphene surface play the role of mediator in the electron transfer between the redox center of GOx and the electrode surface. The functionality of the constructed biosensors has been tested on real samples. The results of the recovery rates showed a satisfying degree of accuracy toward determination of glucose concentration. Examination of the potential interfering species has demonstrated favorable sensitivity and selectivity of the designed biosensor for the detection of glucose.

Physicochemical properties and in vitro cytotoxicity of iron oxide-based nanoparticles modified with antiangiogenic and antitumor peptide A7R.

Superparamagnetic iron oxide-based nanoparticles (SPIONs) are promising carriers as targeted drug delivery vehicles, because they can be guided to their target with the help of an external magnetic field. Functionalization of nanoparticles' surface with molecules, which bind with high affinity to receptors on target tissue significantly facilitates delivery of coated nanoparticles to their targeted site. Here, we demonstrate conjugation of an antiangiogenic and antitumor peptide ATWLPPR (A7R) to SPIONs modified with sebacic acid (SPIONs-SA). Successful conjugation was confirmed by various analytical techniques (FTIR, SERS, SEM-EDS, TEM, TGA). Cell cytotoxicity studies, against two cell lines (HUVEC and MDA-MB-231) indicated that SPIONs modified with A7R reduced HUVEC cell viability at concentrations higher than 0.01 mg Fe/mL, in comparison to cells that were exposed to either the nanoparticles modified with sebacic acid or A7R peptide solely, what might be partially caused by a process of internalization.

Fungal Ferromanganese Mineralisation in Cretaceous Dinosaur Bones from the Gobi Desert, Mongolia.

Well-preserved mycelia of fungal- or saprolegnia-like biota mineralised by ferromanganese oxides were found for the first time in long bones of Late Cretaceous dinosaurs from the Gobi Desert (Nemegt Valley, Mongolia). The mycelia formed a biofilm on the wall of the bone marrow cavity and penetrated the osteon channels of the nearby bone tissue. Optical microscopy, Raman, SEM/EDS, SEM/BSE, electron microprobe and cathodoluminescence analyses revealed that the mineralisation of the mycelia proceeded in two stages. The first stage was early post-mortem mineralisation of the hyphae by Fe/Mn-oxide coatings and microconcretions. Probably this proceeded in a mildly acidic to circumneutral environment, predominantly due to heterotrophic bacteria degrading the mycelial necromass and liberating Fe and Mn sorbed by the mycelia during its lifetime. The second stage of mineralisation, which proceeded much later following the final burial of the bones in an alkaline environment, resulted from the massive precipitation of calcite and occasionally barite on the iron/manganese-oxide-coated mycelia. The mineral phases produced by fungal biofilms colonising the interiors of decaying dinosaur bones not only enhance the preservation (fossilisation) of fungal remains but can also be used as indicators of the geochemistry of the dinosaur burial sites.

pH and substrate effect on adsorption of peptides containing Z and E dehydrophenylalanine. surface-enhanced Raman spectroscopy studies on Ag nanocolloids and electrodes.

The silver substrates and pH dependent surface-enhanced Raman scattering (SERS) spectra of unsaturated derivatives of di- and tripeptides (dehydropeptides) are investigated. Experimental spectra were interpreted with the help of DFT calculations and normal-mode analysis. We choose as objects of our studies modified but natural peptides containing Z or E dehydrophenylalanine (((Z)/(E))ΔPhe) residue to study an effect of the type of the isomer on the interaction between the peptide and silver surfaces in the form of nanocolloidal particles and an electrochemically roughened electrode. We also observed that the SERS profile is sensitive to both the type of the studied SERS active substrate and pH, especially for the adsorption on the silver colloid. In general, all dehydropeptides interact with both SERS substrates upon deprotonation of the C-end of the molecule. The participation of the other fragments of the adsorbates such as the N-terminal amino group and the dehydroresidue is also manifested in the SERS spectra. Their orientation with respect to the silver surfaces is discussed in detail.

A SERS-based pH sensor utilizing 3-amino-5-mercapto-1,2,4-triazole functionalized Ag nanoparticles.

We report the first use of 3-amino-5-mercapto-1,2,4-triazole (AMT) to construct a surface-enhanced Raman scattering (SERS) based pH nano- and microsensor, utilizing silver nanoparticles. We optimize the procedure of homogenous attachment of colloidal silver to micrometer-sized silica beads via an aminosilane linker. Such micro-carriers are potential optically trappable SERS microprobes. It is demonstrated that the SERS spectrum of AMT is strongly dependent on the pH of the surroundings, as the transformation between two different adsorption modes, upright (A form) and lying flat (B form) orientation, is provoked by pH variation. The possibility of tuning the nanosensor working range by changing the concentration of AMT in the surrounding solution is demonstrated. A strong correlation between the pH response of the nanosensor and the AMT concentration in solution is found to be controlled by the interactions between the surface and solution molecules. In the absence of the AMT monomer, the performance of both the nano- and microsensor is shifted substantially to the strongly acidic pH range, from 1.5 to 2.5 and from 1.0 to 2.0, respectively, which is quite unique even for SERS-based sensors.

Exchange of methyl- and azobenzene-terminated alkanethiols on polycrystalline gold studied by tip-enhanced Raman mapping.

Mixed thiol self-assembled monolayers (SAMs) presenting methyl and azobenzene head groups were prepared by chemical substitution from the original single-component n-decanethiol or [4-(phenylazo)phenoxy]hexane-1-thiol SAMs on polycrystalline gold substrates. Static contact-angle measurements were carried out to confirm a change in the hydrophobicity of the functionalized surfaces following the exchange reaction. The mixed SAMs presented contact-angle values between those of the more hydrophobic n-decanethiol and the more hydrophilic [4-(phenylazo)phenoxy]hexane-1-thiol single-component SAMs. By means of tip-enhanced Raman spectroscopy (TERS) mapping experiments, it was possible to highlight that molecular replacement takes place easily and first at grain boundaries: for two different mixed SAM compositions, TERS point-by-point maps with <50 nm step sizes showed different spectral signatures in correspondence to the grain boundaries. An example of the substitution extending beyond grain boundaries and affecting flat areas of the gold surface is also shown.

Interactions of doxorubicin with organized interfacial assemblies. 2. Spectroscopic characterization.

Doxorubicin is an anthracycline that has found wide use as a chemotherapeutic agent, with the primary limitation to its use being cardiotoxicity. Depending on the identity and location of pendent side groups, the anthracyclines exhibit varying degrees of chemotherapeutic activity and toxicity, and a key area of research activity lies in understanding how the structure of the anthracycline influences its interactions with amphiphilic interfaces. We have studied interactions between doxorubicin and interfacial adlayers of octadecylamine (C18NH2), dihexadecylphosphate (DHP), and both monolayers and bilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) on mica using time- and frequency-resolved spectroscopic measurements. We report surface-enhanced resonance Raman data and fluorescence lifetime and anisotropy imaging data for doxorubicin at these interfaces. For all monolayers, there is a substantial interaction between doxorubicin and the interface. For DMPC bilayers, the extent of the interaction between doxorubicin and the interface depends on how the interface was formed.

Comparative studies on IR, Raman, and surface enhanced Raman scattering spectroscopy of dipeptides containing ΔAla and ΔPhe.

Three dipeptides containing dehydroresidues (ΔAla, Δ((Z))Phe, and Δ((E))Phe) were examined by IR, Raman, and surface-enhanced Raman techniques for the first time. The effect of the size and isomer type of the ß-substituent in the dehydroresidue on the conformational structure of the peptide was evaluated by using the analysis of IR and Raman bands. Additionally, SERS spectroscopy provided insight into the adsorption mechanism of these species on the metal surface. SERS spectra were recorded at alkaline pH on the silver sol using visible light excitation. The dehydroresidues studied here strongly influenced the SERS profile of the peptides. The most pronounced SERS signal for all dipeptides was assigned to the symmetric stretching vibration of the carboxylate ions. This indicates that the dehydropeptides studied here primarily adsorb via the deprotonated carboxylic group. Additionally, the enhanced SERS bands in the range 1550-1650 cm(-1) show differences in contribution of the dehydroresidue to the adsorption mechanism of the studied peptides.

[Knowledge of BLS and AED resuscitation algorithm amongst medical students--preliminary results]. / Znajomosc teorii stosowania algorytmu BLS-AED wsród studentów medycyny--doniesienie wstepne.

BACKGROUND: Early recognition of cardiac arrest (CA) and immediate commencement of resuscitation, may increase the survival rate among CA victims. We therefore conducted a survey among medical students to assess their knowledge of BLS and AED. METHODS: The audit was performed among students, most of whom had completed at least one first aid course and those who had not done a first-aid course at all. The ERC-recommended questionnaire 2005 was used for the survey. RESULTS: One hundred and sixty five students completed the survey. Most of them recognized the usefulness of basic resuscitation algorithms and the use of AEDs. 88% of students recognized the importance offirst aid courses, and 91.6% would undertake them again. Despite obvious enthusiasm and self-declared adequate knowledge, 45.7% of the audited students were not familiar with the guidelines and answered wrongly to more than 6 of 12 questions in the questionnaire. The vast majority of the first year medical students were not familiar with the algorithms. CONCLUSION: We conclude that general knowledge of resuscitation algorithms among medical students is inadequate, and regular refresher courses are essential.

Construction of DNA biosensor at glassy carbon surface modified with 4-aminoethylbenzenediazonium salt.

A simple, label-free electrochemical impedance-spectroscopy method for sequence-specific detection of DNA using a 4-aminoethylbenzenediazonium (AEBD) salt as a binder for amino-modified probe DNA is reported. This novel method simplifies the anchoring of DNA at the GC surface and opens new ways for the detection of hybridization. The hybridization of target DNA, without and with mismatches, with the probe DNA anchored at the GC surface modified with AEBD, greatly increases the interfacial electron transfer resistance at the double-stranded DNA modified electrodes for the redox couple Fe(CN)(6)(3-/4-). The resistance was measured using electrochemical impedance spectroscopy. The sensor response increased linearly with logarithm of concentration of target DNA in the range 2×10(-12)÷2×10(-6) M. The obtained quantification limit was circa 6.5×10(-17) mole in a 7 µL droplet and corresponded to a concentration of 9.2×10(-12) M of target DNA in the sample. This limit is equivalent to the detection of circa 4×10(7) copies of DNA in a 7 µL droplet or circa 5.7×10(12) DNA copies in one litre of sample.

Structure and composition of binary monolayers self-assembled from sodium 2-mercaptoetanosulfonate and mercaptoundecanol mixed solutions on silver and gold supports.

Voltammetric reductive desorption, scanning tunneling microscopy (STM) and surface-enhanced Raman scattering (SERS) were used to determine the composition and structure of mixed, two-component monolayers of sodium 2-mercaptoetanosulfonate (MES) and mercaptoundecanol (MUL) on silver and gold supports. Monolayers were prepared by self assembling from ethanolic solutions of varying composition. Preferred adsorption of MUL was found in the electrochemical experiments on Au(111). The presence of two well-separated reductive desorption peaks in the voltammograms of the mixed monolayers on Au(111) indicated the existence of MES-rich and MUL-rich phases in a wide range of solution compositions. STM imaging confirmed formation of a few-nanometer-wide thiol domains for xMES greater than 0.5 in the solution used for SAMs preparation. On the contrary, SERS experiments pointed at dominant adsorption of MES on rough Ag and Au substrates. Nearly exclusive adsorption of the MES for xMES greater than 0.5 was observed on the rough Ag surface.