Selective conversion of aldehydes to functional esters utilizing the Tishchenko reaction

Different modifications of the Tishchenko reaction were studied in order to develop new catalysts and technology to produce 1,3-diol monoester derivatives. Related monoesters are the most common coalescing agents in paint industry with over 100 kilo tonnes total global annual production. The products can also be utilized as solvents and lubricants. During this project a selective process for the preparation of 1,3-diol monoesters with aldol-Tishchenko type mixed Tishchenko reaction via 1,3-dioxan-4-ols was developed and optimized to give a selective and economical method that can be scaled up to industrial scale. The 1,3-dioxan-4-ol type intermediates were initially prepared by dimerization of the isolated β-hydroxy aldehyde and another monofunctional aldehyde. New information concerning the formation, isolation and stability of 1,3-dioxan-4-ol type structures was also obtained. Due to the instability of 1,3-dioxan-4-ol like intermediates the method is temperature sensitive and should be conducted at relatively low temperatures. The catalyst studies in the esterification of 1,3-dioxan-4-ols indicated that the basic nature of the catalyst is essential for the initiation of the reaction. Also sufficient Lewis acidity is required due to the coordination of the counter cation to the oxygens of dioxanol and the formation of the transition state. New 1,3-diol based catalysts were found to give esterification rates of 1,3-dioxan-4-ols faster than previously used metal hydroxides. High yields were obtained without observable product hydrolysis. Another process developed was the homo aldol-Tishchenko reaction of monofunctional enolizable aldehydes to 1,3-diol monoesters under water free reaction conditions. The use of 1,3-diol based monoalcoholate catalysts and one of the formed side products as the solvent provides an advantageous and economical process as the costs due to the formation of wastes are minimized. This work focused on the production of the most important paint industry coalescing agents (2,2-dimethyl-3-hydroxyl-1-isopropyl-propyl)-2-methylpropionate and (3-hydroxy-2,2,4-trimethylpentyl)-2-methylpropionate with the highest yields reported ever. Finally, a new pathway to synthesize a Taxol™ A-ring building block was investigated. In the final step of the synthesis different forms of formaldehyde were utilized successfully as the electrophiles in the Shapiro reaction. The synthesis developed gives the Taxol™ A-ring in good stepwise yields and is clearly superior to the previously described pathways.reviewe

Akuutin sydäninfarktipotilaan hätäkoronaariangiografian tarkistuslistan laatiminen

Keski-Pohjanmaan keskussairaalan sydäntoimenpideyksikkö vastaa sydänpotilaiden invasiivisista sydäntutkimuksista. Yksikössä on valmius tehdä sydämen varjoainekuvauksia ja pallolaajennuksia virka-ajan lisäksi ”hätätöinä” kaikkina vuorokauden aikoina. Nykyisten hoitosuositusten mukaan akuutin sydäninfarktin ensisijaisena hoitomuotona suositellaan sydämen varjoainekuvausta ja mahdollista pallolaajennusta tietyssä aikaikkunassa, mikä vaatii sairaalalta toimivaa hoitoketjua. Työmme tavoitteena on parantaa potilasturvallisuutta sekä parantaa tiedonkulkua päivystyspoliklinikan ja sydäntoimenpideyksikön välillä. Opinnäytetyön tuotoksena laadittiin tarkistuslista, joka tehtiin Keski-Pohjanmaan keskussairaalan pyynnöstä. Tuote on A4-kokoinen yksipuoleinen, selkeä ja helppolukuinen kaavake; mikä tutkimusten mukaan palvelee parhaiten tarkistuslistan käytettävyyttä. Projektina toteutettu opinnäytetyö tehtiin Keski-Pohjanmaan keskussairaalan päivystyspoliklinikalle. Tarkistuslistan sisältö laadittiin heidän toiveidensa mukaan, jotta se palvelisi sairaalaa ja potilaita parhaalla mahdollisella tavalla. Tietoperustassa käsitellään potilasturvallisuutta, tarkistuslistan periaatteita, sydämen toimintaa sekä akuutin sydäntapahtuman hoitoa ja sen toteutusta Keski-Pohjanmaan alueella että Käypä hoito -suositusten mukaisesti. Tuotoksena valmistui tarkistuslista, jota koekäytön pohjalta paranneltiin ja selkeytettiin. Hoitokäytäntöjen kehittyessä tarkistuslistaa on helppo muuntaa tarpeenmukaisesti. Opinnäytetyön valmistuttua tarkistuslista tulee Keski-Pohjanmaan keskussairaalan intranetin hoito-ohjeisiin, josta se on käytettävissä ja tulostettavissa päivystyspoliklinikalle

HYVÄ PERHEVALMENNUS : JYTA-alueen vanhempien ja terveydenhoitajien mielipiteitä perhevalmennuksesta

Opinnäytetyön tarkoitus oli selvittää vanhempien ja perhevalmennusta pitävien terveydenhoitajien kokemuksia tämänhetkisestä perhevalmennuksesta Jyta-alueella. Opinnäytetyö oli työelämälähtöinen. Tavoitteena oli kerätä mahdollisimman paljon parannusehdotuksia vanhemmilta ja terveydenhoitajilta, jotta tulosten pohjalta perhevalmennusta voitaisiin kehittää. Lisäksi haluttiin selvittää, miten monitoimijaista perhevalmennusta voitaisiin hyödyntää enemmän. Tutkimus oli kvantitatiivinen ja aineistonkeruumenetelmänä käytimme kyselylomakkeita. Kyselylomakkeet sisälsivät strukturoitujen kysymysten lisäksi kaksi avointa kysymystä. Otos koostui perhevalmennuksen käyneistä isistä, äideistä ja terveydenhoitajista, joita oli yhteensä 43. Tuloksista kävi ilmi, että miesten ja naisten mielipiteet perhevalmennuksen kokemuksista ja parannusehdotuksista olivat hyvin samankaltaisia. Synnytyskipua ja sen hallintamahdollisuuksia, äidin jaksamista ja jaksamisen tukemista sekä tutustumista synnytyssairaalaan pidettiin erittäin tärkeinä. Myös ohjausta vauvan hoitoon pidettiin yhtenä tärkeimmistä perhevalmennuksen sisältöasioista. Perhevalmennuksen eri vetäjistä äidit, isät ja terveydenhoitajat arvostivat eniten äitiys- ja lastenneuvoloiden terveydenhoitajia sekä muita isejä ja äitejä, jotka osallistuivat perhevalmennukseen. Vanhemmat ja terveydenhoitajat kokivat lääkärin, fysioterapeutin ja psykologin roolin vähiten tärkeiksi. Synnytyksenjälkeistä perhevalmennusta kannattivat lähes kaikki vanhemmat, mutta isistä vain muutama oli valmis osallistumaan siihen. Äideistä puolet oli valmiita osallistumaan vanhempainvalmennukseen. Parannusehdotuksiksi muodostui isien roolien esille nostaminen, vanhempainvalmennus-ryhmä sekä monipuolisempi valmennus, jossa huomioitaisiin enemmän ryhmän erilaista osaamista ja kokemusta.The purpose of this thesis was to discover parent`s experiences of family guidance in JYTA-district. The research was based on work life-needs. Research was conducted from the parent’s point of views and their experiences of family guidance. The future goal is to develop family guidance based on these experiences. The goal was to gather improvement and upgrading suggestions as many as possible from the parents and public health nurses. In addition to this we wanted to find out how to improve cooperation between different professions. The research was quantitative and the method of gathering data was a questionnaire. Questionnaires included among structured questions a couple of open questions. The sample consisted of moms, dads and Public health nurses, the total amount of 43. Results indicate that men’s and women’s opinions about experiences of family guidance and improvement suggestions were very similar. Antenatal pain and the handling of it, mother´s coping and how to support it and exploring the labor hospital were experienced very important points in family guidance. Also guiding how to take care of the baby was considered one of the most important contents matters of family guidance. Moms, dads and Public health nurses appreciated most prenatal clinics public health nurses, children’s health care nurses but also other moms and dads who participated in family guidance. Moms and dads experienced physiotherapist and psychologist the least important in family guidance. Almost every mom and dad supported postnatal family guidance but only a few dads were eager to participate in it. Almost half of the moms were interested to participating in postnatal family guidance. Respondents suggested to improving postnatal family guidance, giving more attention to dads during the family guidance and paying attention to experiences among the group

Fast Aldol-Tishchenko Reaction Utilizing 1,3-Diol Monoalcoholates as the Catalysts

Abstract: The aldol-Tishchenko reaction of enolizable aldehydes is a simple and effective way to prepare 1,3-diol monoesters, which are widely used as coalescing agents in the paint industry. The use of monoalcoholates of 1,3-diols as catalysts gives fast and clean reactions compared with the previous use of several inorganic catalysts. The use of the proper 1,3-diol moiety in the catalyst also reduces the amount of side products which are due to ester interchange between product esters and the catalyst. The rapid water-free method developed herein allows fast preparation of monoesters with excellent yield and minimized formation of side products. Introduction In many cases traditional Tishchenko 1 and aldol-Tishchenko 2 reactions are competitive with each other. 3 However, these reactions can sometimes proceed selectively with the proper choice of catalyst. The aldol-Tishchenko reaction usually requires a basic metal hydroxide catalyst which can activate both aldol reaction and Tishchenko esterification

The Association Between Epigenetic Clocks and Physical Functioning in Older Women: A 3-Year Follow-up

Epigenetic clocks are composite markers developed to predict chronological age or mortality risk from DNA methylation (DNAm) data. The present study investigated the associations between 4 epigenetic clocks (Horvath’s and Hannum’s DNAmAge and DNAm GrimAge and PhenoAge) and physical functioning during a 3-year follow-up.We studied 63- to 76-year-old women (N = 413) from the Finnish Twin Study on Aging. DNAm was measured from blood samples at baseline. Age acceleration (AgeAccel), that is, discrepancy between chronological age and DNAm age, was determined as residuals from linear model. Physical functioning was assessed under standardized laboratory conditions at baseline and at follow-up. A cross-sectional analysis was performed with path models, and a longitudinal analysis was conducted with repeated measures linear models. A nonrandom missing data analysis was performed.In comparison to the other clocks, GrimAgeAccel was more strongly associated with physical functioning. At baseline, GrimAgeAccel was associated with lower performance in the Timed Up and Go (TUG) test and the 6-minute walk test. At follow-up, significant associations were observed between GrimAgeAccel and lowered performance in the TUG, 6-minute and 10-m walk tests, and knee extension and ankle plantar flexion strength tests.The DNAm GrimAge, a novel estimate of biological aging, associated with decline in physical functioning over the 3-year follow-up in older women. However, associations between chronological age and physical function phenotypes followed similar pattern. Current epigenetic clocks do not provide strong benefits in predicting the decline of physical functioning at least during a rather short follow-up period and restricted age range.Peer reviewe

Midlife Cardiovascular Status and Old Age Physical Functioning Trajectories in Older Businessmen

Peer reviewe

Longitudinal Associations of High-Volume and Vigorous-Intensity Exercise With Hip Fracture Risk in Men

Maintenance of vigorous exercise habits from young to old age is considered protective against hip fractures, but data on fracture risk in lifelong vigorous exercisers are lacking. This longitudinal cohort study examined the hazard of hip fractures in 1844 male former athletes and 1216 population controls and in relation to exercise volume and intensity in later years. Incident hip fractures after age 50 years were identified from hospital discharge register from 1972 to 2015. Exercise and covariate information was obtained from questionnaires administered in 1985, 1995, 2001, and 2008. Analyses were conducted using extended proportional hazards regression model for time-dependent exposures and effects. During the mean +/- SD follow-up of 21.6 +/- 10.3 years, 62 (3.4%) athletes and 38 (3.1%) controls sustained a hip fracture. Adjusted hazard ratio (HR) indicated no statistically significant difference between athletes and controls (0.84; 95% confidence interval [CI], 0.55-1.29). In subgroup analyses, adjusted HRs for athletes with recent high (>= 15 metabolic equivalent hours [MET-h]/week) and low (= 6 METs at least 75 minutes/week) had initially 77% lower hazard rate (adjusted HR 0.23; 95% CI, 0.06-0.86) than controls. However, the HR was time-dependent (adjusted HR 1.04; 95% CI, 1.01-1.07); by age 75 years the HRs for the athletes with vigorous-intensity exercise reached the level of the controls, but after 85 years the HRs for these athletes increased approximately 1.3-fold annually relative to the controls. In conclusion, these data suggest that continuation of vigorous-intensity exercise is associated with lower HR of hip fracture up to old age. (c) 2022 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research (ASBMR).Peer reviewe

OR-039 Normal-weight obesity and physical fitness in Chinese university students: an overlooked association

Objective The primary aim of this study was to examine the associations of normal weight obesity with physical fitness in Chinese university students. As a secondary aim, we assessed whether possible differences in physical fitness between students classified as NWO and normal weight non-obese (NWNO) were mediated by skeletal muscles mass. Methods A total of 383 students (205 males and 178 females, aged 18–24 years) from two universities volunteered to participate in this study. Body height and weight were measured by standard procedures and body composition was assessed by a bio-impedance device (InBody 720). NWO was defined by a BMI of 18.5 - 23.9 kg/m2 and a body fat percentage of > 20% and > 30% in male and female students, respectively. Physical fitness was measured using a 10-min intermittent endurance running test (Andersen test), counter movement jumps (CMJ) and a 5 × 5-m shuttle run test (5mSR). The level of leisure time physical activity (PA) was assessed by a questionnaire. Results  13.7% of male and 27.5% of female students were classified as NWO. Compared to NWNO, students classified as NWO showed a significantly poorer performance on the Andersen test (males: 1146 ± 70 m vs. 1046 ± 95 m, females: 968 ± 61 m vs. 907 ± 67m, p < 0.001), CMJ (males: 55.0 ± 7.6 cm vs. 44.9 ± 7.5 cm, females: 39.8 ± 8.0 cm vs. 33.7 ± 5.9 cm, p < 0.001), 5mSR (males: 18.7 ± 1.0 s vs. 20.0 ± 0.9 s, females: 21.1 ± 1.1 s vs. 22.4 ± 1.3 s, p < 0.001), respectively. The lower levels of physical fitness in NWO were partially explained by lower skeletal muscle mass (p < 0.001) both in male and female students Conclusions NWO was associated with poorer physical fitness and the relationship was partially mediated by lower skeletal muscle mass. The study indicated that attention should be paid for the potential hidden health risk in university students with normal body mass index but excessive fat mas

Body Weight, Physical Activity, and Risk of Cancer in Lynch Syndrome

Lynch syndrome (LS) increases cancer risk. There is considerable individual variation in LS cancer occurrence, which may be moderated by lifestyle factors, such as body weight and physical activity (PA). The potential associations of lifestyle and cancer risk in LS are understudied. We conducted a retrospective study with cancer register data to investigate associations between body weight, PA, and cancer risk among Finnish LS carriers. The participants (n = 465, 54% women) self-reported their adulthood body weight and PA at 10-year intervals. Overall cancer risk and colorectal cancer (CRC) risk was analyzed separately for men and women with respect to longitudinal and near-term changes in body weight and PA using extended Cox regression models. The longitudinal weight change was associated with an increased risk of all cancers (HR 1.02, 95% CI 1.00–1.04) and CRC (HR 1.03, 1.01–1.05) in men. The near-term weight change was associated with a lower CRC risk in women (HR 0.96, 0.92–0.99). Furthermore, 77.6% of the participants retained their PA category over time. Men in the high-activity group had a reduced longitudinal cancer risk of 63% (HR 0.37, 0.15–0.98) compared to men in the low-activity group. PA in adulthood was not associated with cancer risk among women. These results emphasize the role of weight maintenance and high-intensity PA throughout the lifespan in cancer prevention, particularly in men with LS