Crystallization Kinetics of Phosphonium Ionic Liquids: Effect of Cation Alkyl Chain Length and Thermal History.

The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid-glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.

Inflection Point in Pressure Dependence of Ionic Conductivity as a Fingerprint of Local Structure Formation.

In this study, we employed dielectric spectroscopy to investigate the effect of temperature and pressure on the ion dynamics of phosphonium ionic liquids (ILs) differing by the length of an alkyl chain, [P666,n][TFSI] (n = 2, 6, 8, 12). We found that both temperature and pressure dependence of dc-conductivity (σdc) determined for all examined ILs herein exhibit unique characteristics, unusual for aprotic ILs. Two regions differing by ion self-organization have been identified from the derivative analysis of σdc(T-1) data. On the other hand, isothermal measurements performed at elevated pressure revealed a unique concave-convex character of σdc(P) dependences, resulting in a clear minimum in the pressure behavior of activation volume. Such an inflection point characterizing the pressure dependence of σdc in [P666,n][TFSI] ILs can be considered an inherent feature of ion dynamics governed by structural self-assembly. Our results offer a unique perspective to link the ion mobility at various T-P conditions to the nanostructural organization of ionic systems.

Non-Isochronal Behavior of Charge Transport at Liquid-Liquid and Liquid-Glass Transition in Aprotic Ionic Liquids.

A reversible, first-order transition separating two liquid phases of a single-component material is a fascinating yet poorly understood phenomenon. Here, we investigate the liquid-liquid transition (LLT) ability of two tetraalkylphosphonium ionic liquids (ILs), [P666,14]Cl and [P666,14][1,2,4-triazolide], using differential scanning calorimetry and dielectric spectroscopy. The latter technique also allowed us to study the LLT at elevated pressure. We found that cooling below 205 K transforms [P666,14]Cl and [P666,14][Trz] from one liquid state (liquid 1) to another (the self-assembled liquid 2), while the latter facilitates the charge transport decoupled from structural dynamics. In contrast to temperature, pressure was found to play an essential role in the self-organization of a liquid 2 phase, resulting in different time scales of charge transport for rapidly and slowly compressed samples. Furthermore, τσ(PLL) was found to be much shorter than τσ(TLL, P=atm), which constitutes the first example of non-isochronal behavior of charge transport at LLT. In turn, dielectric studies through the liquid-glass transition revealed the non-monotonic behavior of τσ at elevated pressure for [P666,14]Cl, while for [P666,14][Trz] τσ(Pg) was almost constant. These results highlight the diversity of liquid-liquid transition features within the class of phosphonium ionic liquids.

Correction: Naked and necked gold nanoparticles prepared by submerged alternating current arc discharge in water.

[This corrects the article DOI: 10.1039/D2RA06050G.].

Necked gold nanoparticles prepared by submerged alternating current arc discharge in water.

The article presents the method of producing gold nanoparticles using a high voltage arc discharge of alternating current with a frequency of 50 Hz in distilled water. The equipment necessary to carry out the process is described, including the construction of the reactor and the power source of a very simple design necessary to generate a high-voltage arc discharge between the electrodes. Arc discharge processes were carried out two times for 2 and 5 minutes, respectively, in ambient conditions without thermostating the reactor, at medium temperature varying in the range of 25-70 °C. The obtained gold nanoparticles were examined by means of various analytical techniques such as UV-vis spectroscopy, zeta potential measurement, energy dispersive X-ray analysis (EDS), X-ray diffraction (XRD). The morphology, surface, and size of the obtained nanoparticles were carried out using transmission electron microscopy (HRTEM) and dynamic light scattering (DLS). The concentration of the obtained colloids were determined using the mass spectrometry ICP-MS technique. The results show that high-voltage AC arc discharge is a simple and effective way to obtain stable gold nanoparticles under environmentally friendly conditions at relatively low production costs, and can be considered as an alternative to arc discharge nanoparticles synthesis by means of direct current (DC) methods.

The effect of in-situ decompression on ulnar nerve stability: a cadaveric study.

Ten fresh frozen right cadaver arms were placed in a motorized jig and an in-situ ulnar nerve decompression was performed in 5 mm increments distally to the flexor carpi ulnaris (FCU) aponeurosis then proximally to the intermuscular septum. The elbows were ranged 0-135° after each incremental decompression and the ulnar nerve to medial epicodyle distance was measured to assess for nerve translation/subluxation compared with baseline (prerelease) values. None of the specimens had ulnar nerve subluxation (defined as anterior translation past the medial epicondyle) even after full decompression. Furthermore, there were no statistically significant ulnar nerve translations (defined as any difference in distance from ulnar nerve to medial epicondyle before and after each decompression) for any flexion angle or extent of decompression. This study provides biomechanical evidence that in situ ulnar nerve decompression from the FCU aponeurosis to the intermuscular septum does not result in significant ulnar nerve translation or subluxation.

Predictors of outcome for telephone and face-to-face administered cognitive behavioral therapy for depression.

BACKGROUND: Cognitive behavioral therapy (CBT) can be delivered efficaciously through various modalities, including telephone (T-CBT) and face-to-face (FtF-CBT). The purpose of this study was to explore predictors of outcome in T-CBT and FtF-CBT for depression. METHOD: A total of 325 depressed participants were randomized to receive eighteen 45-min sessions of T-CBT or FtF-CBT. Depression severity was measured using the Hamilton Depression Rating Scale (HAMD) and the Patient Health Questionnaire-9 (PHQ-9). Classification and regression tree (CART) analyses were conducted with baseline participant demographics and psychological characteristics predicting depression outcomes, HAMD and PHQ-9, at end of treatment (week 18). RESULTS: The demographic and psychological characteristics accurately identified 85.3% and 85.0% of treatment responders and 85.7% and 85.0% of treatment non-responders on the HAMD and PHQ-9, respectively. The Coping self-efficacy (CSE) scale predicted outcome on both the HAMD and PHQ-9; those with moderate to high CSE were likely to respond with no other variable influencing that prediction. Among those with low CSE, depression severity influenced response. Social support, physical functioning, and employment emerged as predictors only for the HAMD, and sex predicted response on the PHQ-9. Treatment delivery method (i.e. telephone or face-to-face) did not impact the prediction of outcome. CONCLUSIONS: Findings suggest that the predictors of improved depression are similar across treatment modalities. Most importantly, a moderate to high level of CSE significantly increases the chance of responding in both T-CBT and FtF-CBT. Among patients with low CSE, those with lower depressive symptom severity are more likely to do well in treatment.

Efficacy of a sun protection workbook for kidney transplant recipients: a randomized controlled trial of a culturally sensitive educational intervention.

A culturally sensitive educational intervention that encouraged sun protection behaviors among kidney transplant recipients (KTRs) was developed and the short-term efficacy was evaluated. Non-Hispanic White, Hispanic/Latino and non-Hispanic Black patients, who received a transplant 2-24 months prior to the study, were randomized into two study groups: intervention versus standard of care. Electronic reminders tailored to the weather conditions were sent every 2 weeks by text message or email. Self-reported surveys and biologic measurements were obtained prior to the intervention and 6 weeks later. Among the 101 study participants, there was a statistically significant increase in knowledge, recognition of personal risk of developing skin cancer, willingness to change sun protection behavior and self-reported performance of sun protection in participants receiving the intervention in comparison with those receiving standard of care (p < 0.05). The pigment darkening of the sun-exposed forearm and sun damage of the forearm and sunburns/skin irritation from the sun were significantly less in participants receiving the intervention (p < 0.05). Providing sun protection education at the beginning of summer with reminders tailored to weather conditions helped KTRs adopt sun protection practices. This sun protection program for KTRs may be incorporated into the care provided by the nephrologist or transplant surgeon.

Back to the basics: regular exercise matters in parkinson's disease: results from the National Parkinson Foundation QII registry study.

BACKGROUND: There is a substantial interest in the impact of exercise on reduction of disability and rate of progression of Parkinson's disease (PD). OBJECTIVE: The primary aim was to describe exercise habits of PD patients and factors associated with greater levels of exercise. The secondary aim was to explore whether regular exercise is associated with a slower decline of function, disease-related quality of life, and caregiver burden. METHODS: The National Parkinson's Foundation (NPF) QII Registry data was used to analyze variables that correlate with levels of exercise in PD patients across disease severity. Subjects were categorized into three groups: non-exercisers (0 min/week), low exercisers (1-150 min/week), and regular exercisers (>150 min/week). Health related outcomes, disease metrics, and demographic factors associated with exercise were examined using bivariate analyses. Multiple regression models controlled for disease duration, severity, and cognitive function. An exploratory analysis was completed on the association of baseline level of exercise with health outcomes at one year follow up. RESULTS: 4866 subjects were included in the baseline analysis and 2252 subjects who had second visits were included in the longitudinal data. Regular exercisers at baseline were associated with better QOL, mobility, and physical function, less progression of disease, less caregiver burden and less cognitive decline one year later, after controlling for demographic and disease severity variables. CONCLUSIONS: This study provides important preliminary evidence of the beneficial effects of regular exercise in a large PD cohort. Longitudinal studies will be essential to confirm findings.

Blood transcriptomic biomarkers in adult primary care patients with major depressive disorder undergoing cognitive behavioral therapy.

An objective, laboratory-based diagnostic tool could increase the diagnostic accuracy of major depressive disorders (MDDs), identify factors that characterize patients and promote individualized therapy. The goal of this study was to assess a blood-based biomarker panel, which showed promise in adolescents with MDD, in adult primary care patients with MDD and age-, gender- and race-matched nondepressed (ND) controls. Patients with MDD received cognitive behavioral therapy (CBT) and clinical assessment using self-reported depression with the Patient Health Questionnaire-9 (PHQ-9). The measures, including blood RNA collection, were obtained before and after 18 weeks of CBT. Blood transcript levels of nine markers of ADCY3, DGKA, FAM46A, IGSF4A/CADM1, KIAA1539, MARCKS, PSME1, RAPH1 and TLR7, differed significantly between participants with MDD (N=32) and ND controls (N=32) at baseline (q< 0.05). Abundance of the DGKA, KIAA1539 and RAPH1 transcripts remained significantly different between subjects with MDD and ND controls even after post-CBT remission (defined as PHQ-9 <5). The ROC area under the curve for these transcripts demonstrated high discriminative ability between MDD and ND participants, regardless of their current clinical status. Before CBT, significant co-expression network of specific transcripts existed in MDD subjects who subsequently remitted in response to CBT, but not in those who remained depressed. Thus, blood levels of different transcript panels may identify the depressed from the nondepressed among primary care patients, during a depressive episode or in remission, or follow and predict response to CBT in depressed individuals.

Do positive or negative stressful events predict the development of new brain lesions in people with multiple sclerosis?

BACKGROUND: Stressful life events have long been suspected to contribute to multiple sclerosis (MS) disease activity. The few studies examining the relationship between stressful events and neuroimaging markers have been small and inconsistent. This study examined whether different types of stressful events and perceived stress could predict the development of brain lesions. METHOD: This was a secondary analysis of 121 patients with MS followed for 48 weeks during a randomized controlled trial comparing stress management therapy for MS (SMT-MS) to a waitlist control (WLC). Patients underwent magnetic resonance imaging (MRI) scans every 8 weeks. Every month, patients completed an interview measure assessing stressful life events and self-report measures of perceived stress, anxiety and depressive symptoms, which were used to predict the presence of gadolinium-enhancing (Gd+) and T2 lesions on MRI scans 29-62 days later. Participants classified stressful events as positive or negative. Negative events were considered 'major' if they involved physical threat or threat to the patient's family structure, and 'moderate' otherwise. RESULTS: Positive stressful events predicted decreased risk for subsequent Gd+ lesions in the control group [odds ratio (OR) 0.53 for each additional positive stressful event, 95% confidence interval (CI) 0.30-0.91] and less risk for new or enlarging T2 lesions regardless of group assignment (OR 0.74, 95% CI 0.55-0.99). Across groups, major negative stressful events predicted Gd+ lesions (OR 1.77, 95% CI 1.18-2.64) and new or enlarging T2 lesions (OR 1.57, 95% CI 1.11-2.23) whereas moderate negative stressful events, perceived stress, anxiety and depressive symptoms did not. CONCLUSIONS: Major negative stressful events predict increased risk for Gd+ and T2 lesions whereas positive stressful events predict decreased risk.

Halometallate ionic liquids--revisited.

Ionic liquids with chlorometallate anions may not have been the first ionic liquids, however, it was their development that lead to the recognition that ionic liquids are a distinct, and useful, class of (functional) materials. While much of the phenomenal interest and attention over the past two decades has focussed on 'air and water stable' ionic liquids, research and application of chlorometallate systems has continued unabated albeit largely out of the main spotlight. The defining characteristic of chlorometallates is the presence of complex anionic equilibria, which depend both on the type and on the concentration of metal present, and leads directly to their characteristic and individual properties. Here, we review the experimental techniques that can be applied to study and characterise the anion speciation in these ionic liquids and, using recent examples, illustrate how their applications base is evolving beyond traditional applications in Lewis acidic catalysis and electrochemistry through to uses as soft and component materials, in the ionothermal synthesis of semiconductors, gas storage systems and key components in the development of biomass processing.

Caregiver strain in Parkinson's disease: national Parkinson Foundation Quality Initiative study.

BACKGROUND: National Parkinson Foundation Quality Improvement Initiatives (NPF-QII) is the first large scale data-driven initiative in Parkinson's disease (PD) aimed at identifying variables predicting best care models and outcomes. OBJECTIVE: To determine what measures of PD disability, demographics, and patient quality of life are associated with caregiver strain among caregivers of patients with PD. METHODS: All PD patients at 18 participating sites are eligible for enrollment into the NPF-QII registry. Dataset includes multidimensional measures of disease severity, health care utilization, PD quality of life questionnaire-39 (PDQ-39) and multidimensional caregiver strain inventory (MCSI). A univariate as well as an adjusted analysis was performed to examine the relationship between caregiver strain and variables of PD disability. RESULTS: The single best factor associated with high caregiver strain was the PDQ-39 total score (c-statistic of continuous variable = 0.792, p < 0.001) followed by the PDQ-mobility subscore (c = 0.776, p < 0.001). PDQ-39 ≥ 47 was the optimal cut off associated with a high caregiver strain with a sensitivity = 83% and specificity = 64%. A multiple logistic regression model with stepwise selection showed that in addition to PDQ-39 ≥ 47 (OR and 95% confidence interval = 5.1 (3.2, 8.2), the following subject characteristics were associated with high caregiver strain: (model p < 0.001, c = 0.838): Hoehn and Yahr stage >3 (2.0 (1.3, 3.1)), presence of concomitant medications such as antidepressants (2.1 (1.5, 3.1)) and antipsychotics (2.5 (1.5, 4.2)), social worker visits (1.6 (1.2, 2.1)), male gender (2.3 (1.5, 3.5)), and decreased verbal fluency (0.95 (0.92, 0.98)). CONCLUSIONS: There is a high prevalence of caregiver strain in PD. PDQ-39 total score has the strongest association with high levels of caregiver strain. These results could guide clinicians in the assessment of caregivers at risk.

Patient reported outcomes and analgesia use in osteoarthritis of the knee.

OBJECTIVE: Non-opioid analgesics (NOAs) are widely used to palliate osteoarthritis (OA) pain, however, their role in health-related quality of life (HRQoL) in OA has not been well studied. Here, we assess the relationship of pain, physical function, and HRQoL to NOA use in symptomatic knee OA. METHODS: NOA dose, pain, physical function, and HRQoL were evaluated longitudinally over 1 year in medial knee OA. Doses provided by subjects' weekly medication diaries were normalized to equi-analgesic ibuprofen-equivalents (IEs). Descriptive analyses at baseline, 1.5, and 12 months, and non-parametric comparisons of NOA with pain, physical function, and HRQoL at 1.5 months and over 12 months were performed. RESULTS: Seventy-one subjects (19 males and 52 females; mean 57+/-10.5 years) used an overall median of 300 mg/week of IE. Twenty-five subjects reported no analgesic use during the study; of the 46 subjects that reported NOA use, the median intake was 1325 mg/week IE. Whereas age, Physical Functioning (PF) and HRQoL were predictive of NOA dose both at 1.5 months and during the entire study, pain level was not. The median NOA dose declined over 12 months (P=0.02), however, the change was not associated with changes in PF, HRQoL or pain. CONCLUSION: Greater age and worse physical function and HRQoL, but not pain severity, are predictive of NOA use in symptomatic knee OA. Longitudinally, NOA use does not change as a function of pain. These data suggest that pain is not the primary determinant of NOA use over time among OA patients.

Determination of 5-aminolevulinic acid (ALA) by HPLC method.

5-Aminolevulinic acid is at present most popular precursor of photosensitizer for photodynamic therapy and diagnostics. The effect of accumulation of PpIX induced by exogenous ALA is based on the avoidance of feedback control in the pathway of heme biosynthesis. For use ALA in medicine, development of analytical methods that will enable precise determination of content and purity is necessary. The ALA content is determined i. a. by titration with perchloric acid. Much greater problems are connected with purity determination by HPLC method. There are rather scarce literature data concerning purity determination of ALA by HPLC.

[Safety of laser use]. / Bezpieczenstwo stosowania laserów.

The paper presents the problems related to safe use of lasers being the parts of medical devices. There were discussed laser radiation interaction on biological tissues, hazards that arise during the work with laser devices, as well as fundamental safety rules and obligatory radiation protection standards. The selected constructions of anti-laser filters used for eyesight protection were also presented.

Protoporphyrin derivatives--the use in localization of neoplasmas by titanium laser-induced fluorescence technique.

Examples of in vivo detection of skin neoplasmas (Mercl, melanoma) and breast carcinoma using laser induced fluorescence (LIF) and bis-1[1-alanylo-N]-ethylodeuteroporphyrin (Ala-PP) are described in this study. Photosensitizer, wave titanium laser and standard CCD camera coupled to vision amplifier enable precise neoplasm imaging, Ala-PP retention monitoring and further photodynamic therapy (PDT).

[Phthalocyanines as photosensitizers in the photodynamic method of the treatment of neoplasms]. / Ftalocyjaniny jako fotosensybilizatory w fotodynamicznej metodzie terapii nowotworów.

Photodynamic therapy of tumors with phthalocyanines (PC) as photosensitizers is described. PC may be good alternatives to hematoporphyrin derivatives. The photochemistry and photophysics of the phthalocyanines is reviewed. Emphasis is placed on the effects of PC structure and aggregation state on photosensitized processes in vivo and in vitro.