Calculating average surface enhancement factors of randomly nanostructured electrodes by a combination of SERS and impedance spectroscopy

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Polyhedron Ag nanostructures were created on top of a polished Au electrode via step-wise electrodeposition and tested as substrates for SERS spectroscopy. Average Raman enhancement factors were derived by combining SERS measurements with electrochemical impedance spectroscopy (EIS), which is able to determine the electroactive surface area of a randomly nanostructured surface. Depending on the deposition step an alternating increase and decrease of surface area was observed while the SERS intensity showed a clear maximum for the first deposition cycle. SEM pictures reveal the formation of Ag polyhedrons that are randomly dispersed on the Au surface. Furthermore the presence of a sub nanostructure on top of the polyhedron after the first deposition cycle is observed which becomes smoother after subsequent deposition cycles. Correlating the SEM pictures with SERS and EIS measurements it is concluded that the coral-like sub nanostructure is dominating the enhancement factor while the polyhedron structure itself only plays a minor role for electromagnetic field enhancement.DFG, EXC 314, Unifying Concepts in CatalysisDFG, GSC 1013, School of Analytical Sciences Adlershof (SALSA

Synchrony in psychotherapy: High physiological positive concordance predicts symptom reduction and negative concordance predicts symptom aggravation

Objective Therapeutic alliance is often considered as a predictor for therapeutic success. This study explored dyadic synchrony of skin conductance response (SCR) during naturalistic therapeutic interactions and investigated its potential as an objective biomarker for predicting therapy effectiveness. Methods In this proof-of-concept study, skin conductance from both dyad members was continuously measured via wristbands during psychotherapy. Patients and therapists completed post-session reports capturing their subjective appraisal of therapeutic alliance. Additionally, patients completed symptom questionnaires. Each therapeutic dyad was recorded twice in a follow-up design. The first session of the follow-up group was assessed for physiological synchrony (Single Session Index (SSI)). Therapy outcome was captured by the difference between symptom severity scores over time. Results SCR synchrony significantly predicted the outcome variable of change in patients' global severity index (GSI). High positive SCR concordance was linked to a reduction in patients' GSI, while negative or small positive SSI values were linked to an increase in patients' GSI. Conclusion The results demonstrate the presence of SCR synchrony in clinical interactions. Skin conductance response synchrony was a significant predictor for change in patients' symptom severity index, emphasizing its potential as an objective biomarker in the context of evidence-based psychotherapy

Ultra‐long lived luminescent triplet excited states in cyclic (alkyl)(amino)carbene complexes of Zn(II) halides

The high element abundance and d10 electron configuration make ZnII-based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and -chemical properties of a series of dimeric and monomeric ZnII halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(μ-X)2ZnX(cAAC)] (X=Cl (1), Br (2), I (3)) and [ZnX2(cAAC)(NCMe)] (X=Br (4), I (5)) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo-induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra-long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from 3XCT/LEcAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of ZnII phosphorescent complexes

Approach to canine paroxysmal dyskinesias

The term ‘paroxysmal dyskinesia’ (PD) describes a manifestation of involuntary movement or muscle tone, which by definition is episodic in nature and self-limiting. The PDs remain poorly understood and frequently under-recognised conditions in veterinary patients. The purpose of this article is to review the basic classification and principles of recognition and diagnosis of PDs. This article introduces some of the breed-specific PDs, as well as the treatment/management options available and expected outcomes

Characterization of long and stable de novo single alpha-helix domains provides novel insight into their stability

Naturally-occurring single α-helices (SAHs), are rich in Arg (R), Glu (E) and Lys (K) residues, and stabilized by multiple salt bridges. Understanding how salt bridges promote their stability is challenging as SAHs are long and their sequences highly variable. Thus, we designed and tested simple de novo 98-residue polypeptides containing 7-residue repeats (AEEEXXX, where X is K or R) expected to promote salt-bridge formation between Glu and Lys/Arg. Lys-rich sequences (EK3 (AEEEKKK) and EK2R1 (AEEEKRK)) both form SAHs, of which EK2R1 is more helical and thermo-stable suggesting Arg increases stability. Substituting Lys with Arg (or vice versa) in the naturally-occurring myosin-6 SAH similarly increased (or decreased) its stability. However, Arg-rich de novo sequences (ER3 (AEEERRR) and EK1R2 (AEEEKRR)) aggregated. Combining a PDB analysis with molecular modelling provides a rational explanation, demonstrating that Glu and Arg form salt bridges more commonly, utilize a wider range of rotamer conformations, and are more dynamic than Glu–Lys. This promiscuous nature of Arg helps explain the increased propensity of de novo Arg-rich SAHs to aggregate. Importantly, the specific K:R ratio is likely to be important in determining helical stability in de-novo and naturally-occurring polypeptides, giving new insight into how single α-helices are stabilized

High pressure CO2 CCS pipelines: Comparing dispersion models with multiple experimental datasets

Carbon capture and storage (CCS) presents the short-term option for significantly reducing the amount of carbon dioxide (CO2) released into the atmosphere from the combustion of fossil fuels, thereby mitigating the effects of climate change. Enabling CCS requires the development of capture, storage and transport methodologies. The safe transport of CO2 in CCS scenarios can be achieved through pipelines or by shipping. Either way, transport and temporary storage of pressurised liquid CO2 will be required and subject to quantitative risk assessment, which includes the consideration of the low-risk, low-probability puncture or rupture scenario of such a pipeline, ship or storage facility. In this work, we combine multiple experimental datasets all concerned with the atmospheric free release of pure and impure liquid CO2 from CCS-transport-chain-relevant high pressure reservoirs and perform the first multiple dataset comparison to numerical models for both pure and impure jets in dry ambient air with no water vapour. The results validate the numerical approach adopted and for the prediction of such releases, highlight the significance of the mixture fraction at the release point, over the mixture composition itself. A new method for impure CO2 dispersion modelling is introduced and limited preliminary comparisons of impure CO2 data and predictions are performed. No clear difference between pure and impure releases is found for the cases considered