Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solvent-free conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf)(3) and Hf(OTf)(4), is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.Peer reviewe

Cross-Cultural Adaptation and Validation of the Finnish Version of the Michigan Hand Outcomes Questionnaire

Background and Aims: Michigan Hand Outcomes Questionnaire is a widely used patient-reported outcome measure in hand surgery. The aim of this study was to translate and validate the Michigan Hand Outcomes Questionnaire into Finnish for Finnish patients with hand problems following international standards and guidelines. Material and Methods: The original English Michigan Hand Outcomes Questionnaire was translated into Finnish. Altogether, 115 patients completed the Finnish Michigan Hand Outcomes Questionnaire, and reference outcomes: Disabilities of the Arm and Shoulder, EQ-5D 3L and pain intensity on a visual analog scale. Grip and key pinch forces were measured. After 1-2 weeks, 63 patients completed the Finnish Michigan Hand Outcomes Questionnaire the second time. The Michigan Hand Outcomes Questionnaire was analyzed for internal consistency, repeatability, correlations with the reference outcomes, and factor analysis. Results: Cronbach's alpha ranged from 0.90 to 0.97 in all the Michigan Hand Outcomes Questionnaire subscales, showing high internal consistency. The intraclass correlation coefficient showed good to excellent test-retest reliability ranging from 0.66 to 0.91 in all the Michigan Hand Outcomes Questionnaire subscales. In factor analysis, the structure with six subscales was not confirmed. All the subscales correlated with Disabilities of the Arm and Shoulder score, and five subscales correlated with EQ-5D index. Conclusion: The Finnish version of the Michigan Hand Outcomes Questionnaire showed similar properties compared to the original English version and thus can be used as patient-reported outcome measure for Finnish patients with hand problems.Peer reviewe

Microscopic Black Hole Pairs in Highly-Excited States

We consider the quantum mechanics of a system consisting of two identical, Planck-size Schwarzschild black holes revolving around their common center of mass. We find that even in a very highly-excited state such a system has very sharp, discrete energy eigenstates, and the system performs very rapid transitions from a one stationary state to another. For instance, when the system is in the 100th excited state, the life times of the energy eigenstates are of the order of $10^{-30}$ s, and the energies of gravitons released in transitions between nearby states are of the order of $10^{22}$ eV.Comment: 22 pages, 3 figures, uses RevTe

Reliability and Validity of The Finnish Version of The Boston Carpal Tunnel Questionnaire among Surgically Treated Carpal Tunnel Syndrome Patients

Background and Aims: The Boston Carpal Tunnel Questionnaire is the most commonly used outcome measure in the assessment of carpal tunnel syndrome. The purpose of this study was to translate the original Boston Carpal Tunnel Questionnaire into Finnish and validate its psychometric properties. Materials and Methods: We translated and culturally adapted the Boston Carpal Tunnel Questionnaire into Finnish. Subsequently, 193 patients completed the Finnish version of the Boston Carpal Tunnel Questionnaire, 6-Item CTS Symptoms Scale, and EuroQol 5 Dimensions 12 months after carpal tunnel release. The Boston Carpal Tunnel Questionnaire was re-administered after a 2-week interval. We calculated construct validity, internal consistency, test-retest reliability, and coefficient of repeatability. We also examined floor and ceiling effects. Results: The cross-cultural adaptation required only minor modifications to the questions. Both subscales of the Boston Carpal Tunnel Questionnaire (Symptom Severity Scale and Functional Status Scale) correlated significantly with the CTS-6 and EuroQol 5 Dimensions, indicating good construct validity. The Cronbach's alpha was 0.93 for both the Symptom Severity Scale and Functional Status Scale, indicating high internal consistency. Test-retest reliability was excellent, with an intraclass correlation coefficient greater than 0.8 for both scales. The coefficient of repeatability was 0.80 for the Symptom Severity Scale and 0.68 for the Functional Status Scale. We observed a floor effect in the Functional Status Scale in 28% of participants. Conclusion: Our study shows that the present Finnish version of the Boston Carpal Tunnel Questionnaire is reliable and valid for the evaluation of symptom severity and functional status among surgically treated carpal tunnel syndrome patients. However, owing to the floor effect, the Functional Status Score may have limited ability to detect differences in patients with good post-operative outcomes.Peer reviewe

Black hole area quantization

It has been argued by several authors that the quantum mechanical spectrum of black hole horizon area must be discrete. This has been confirmed in different formalisms, using different approaches. Here we concentrate on two approaches, the one involving quantization on a reduced phase space of collective coordinates of a Black Hole and the algebraic approach of Bekenstein. We show that for non-rotating, neutral black holes in any spacetime dimension, the approaches are equivalent. We introduce a primary set of operators sufficient for expressing the dynamical variables of both, thus mapping the observables in the two formalisms onto each other. The mapping predicts a Planck size remnant for the black hole.Comment: 7 pages, uses MPLA style file (included). Revised version with changes in notation for clarity and consistency. To appear in MPL

Transcriptional Regulation of Quinoa Seed Quality: Identification of Novel Candidate Genetic Markers for Increased Protein Content

Quinoa (Chenopodium quinoa Willd.) is a crop that has great potential for increased cultivation in diverse climate regions. The seed protein quality obtained from this crop is high concerning the requirements to meet human nutritional needs, but the seed protein content is relatively low if compared to crops such as grain legumes. Increased seed protein content is desirable for increasing the economic viability of this crop in order for it to be used as a protein crop. In this study, we characterized three genotypes of quinoa with different levels of seed protein content. By performing RNA sequencing of developing seeds, we determined the genotype differences in gene expression and identified genetic polymorphisms that could be associated with increased protein content. Storage nutrient analyses of seeds of three quinoa genotypes (Titicaca, Pasankalla, and Regalona) from different ecoregions grown under controlled climate conditions showed that Pasankalla had the highest protein content (20%) and the lowest starch content (46%). Our seed transcriptome analyses revealed highly differentially expressed transcripts (DETs) in Pasankalla as compared to the other genotypes. These DETs encoded functions in sugar transport, starch and protein synthesis, genes regulating embryo size, and seed transcription factors. We selected 60 genes that encode functions in the central carbon metabolism and transcription factors as potential targets for the development of high-precision markers. Genetic polymorphisms, such as single nucleotide polymorphisms (SNPs) and base insertions and deletions (InDels), were found in 19 of the 60 selected genes, which can be further evaluated for the development of genetic markers for high seed protein content in quinoa. Increased cultivation of quinoa can contribute to a more diversified agriculture and support the plant protein diet shift. The identification of quinoa genotypes with contrasting seed quality can help establish a model system that can be used for the identification of precise breeding targets to improve the seed quality of quinoa. The data presented in this study based on nutrient and transcriptome analyses contribute to an enhanced understanding of the genetic regulation of seed quality traits in quinoa and suggest high-precision candidate markers for such traits

Application of the FACE-Q rhinoplasty module in a mixed reconstructive and corrective rhinoplasty population in Finland

The FACE-Q Rhinoplasty module is a patient-reported outcome instrument developed for the assessment of primarily aesthetic outcomes of rhinoplasty. The aim of our study was to produce a Finnish version of the instrument and validate it for use in patients undergoing nasal reconstruction as well as those treated with a rhinoplasty. Finnish versions of the FACE-Q scales Satisfaction with Nose, Satisfaction with Nostrils and Adverse Effects: Nose, were translated following established guidelines. Patients undergoing nasal resection, reconstruction or rhinoplasty in Helsinki University Hospital plastic surgery department in 2009-2019 were identified using theatre records. A total of 240 Finnish-speaking patients 18-85 years old were approached with a postal survey questionnaire. The questionnaire included the translated FACE-Q modules and those for Satisfaction with Facial Appearance, Appearance-Related Psychosocial Distress and Satisfaction with Outcome, as well as the general health-related quality of life instrument 15 D. The FACE-Q scales translated readily to Finnish. Eighty-three patients (35%) responded to the survey. Most FACE-Q scales performed well with high internal consistency (Cronbach's alphas 0.87-0.92) and repeatability. Only the Adverse Effects: Nose scale displayed poor consistency and a floor effect with 18% of the patients reporting no adverse outcomes. Answers to the Appearance-Related Psychosocial Distress scale were skewed towards no experienced stress. Answers to the other scales were normally distributed with weak correlation with 15 D dimensions. The Finnish translations of the FACE-Q Rhinoplasty scales perform well at assessing a diverse group of patients including those undergoing nasal reconstruction as well as those undergoing rhinoplasty.Peer reviewe

Lymphatic endothelium stimulates melanoma metastasis and invasion via MMP14-dependent Notch3 and b1-integrin activation

Lymphatic invasion and lymph node metastasis correlate with poor clinical outcome in melanoma. However, the mechanisms of lymphatic dissemination in distant metastasis remain incompletely understood. We show here that exposure of expansively growing human WM852 melanoma cells, but not singly invasive Bowes cells, to lymphatic endothelial cells (LEC) in 3D co-culture facilitates melanoma distant organ metastasis in mice. To dissect the underlying molecular mechanisms, we established LEC co-cultures with different melanoma cells originating from primary tumors or metastases. Notably, the expansively growing metastatic melanoma cells adopted an invasively sprouting phenotype in 3D matrix that was dependent on MMP14, Notch3 and β1-integrin. Unexpectedly, MMP14 was necessary for LEC-induced Notch3 induction and coincident β1-integrin activation. Moreover, MMP14 and Notch3 were required for LEC-mediated metastasis of zebrafish xenografts. This study uncovers a unique mechanism whereby LEC contact promotes melanoma metastasis by inducing a reversible switch from 3D growth to invasively sprouting cell phenotype

Immune activation in the small intestine in patients with rheumatoid arthritis

Objectives: To determine whether inflammation in the gut associated immune system is activated in rheumatoid arthritis ( RA). The expression of chemokine receptor- (CCR4, CCR5) and cytokine- ( interleukin (IL) 2, IL10, interferon gamma (IFNgamma), tumour necrosis factor alpha (TNFalpha), and transforming growth factor beta (TGFbeta)) specific mRNA in intestinal biopsy samples from patients with RA was examined. Methods: Duodenal biopsy samples from 13 patients with RA and 15 control subjects were studied. The mRNA expression of CCR4, CCR5, IL2, IL10, IFNgamma, TNFalpha, and TGFb in intestinal biopsy samples was demonstrated by real time quantitative reverse transcriptase-polymerase chain reaction. Results: The mRNA expression of CCR4, CCR5, and IL10 in intestinal biopsy samples was increased in patients with RA in comparison with control subjects ( p = 0.001, p = 0.046, p = 0.019). No difference in the expression levels of IL2, IFNgamma, TNFalpha, or TGFbeta was seen between patients with RA and controls. Conclusions: The increased intestinal mRNA expression of IL10, CCR5, and CCR4 suggests that gut associated immune cells are activated in patients with RA.Peer reviewe