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1.
Mass Spectrom Rev ; 2023 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-37533397

RESUMO

This article reviews the analytical tool chest used for characterizing alkoxylates and their associated copolymer mixtures. Specific emphasis will be placed upon the use of mass spectrometry-based techniques as rapid characterization tools for optimizing reaction processes in an industrial R&D setting. An initial tutorial will cover the use of matrix-assisted laser desorption/ionization-mass spectrometry and tandem mass spectrometry fragmentation for detailed component analysis (e.g., polyol and isocyanate) of a model polyurethane-based foam. Next, this critical feedback information will be used with the guidance of mass spectrometry to initiate the development of a new, more efficient, tris(pentafluorophenyl)borane (FAB) catalyst-based alkoxylation process for generating the next generation of glycerin-initiated poly(propylene oxide)-co-poly(ethylene oxide) copolymers. Examples will be provided for each step in the FAB-based optimization process that were required to generate the final product. Following this example, two-dimensional liquid chromatography, supercritical fluid chromatography, and ion mobility separations, along with their coupling to mass spectrometry, will be reviewed for their efficiency in characterizing and quantitating the components within these complex polyether polyol mixtures.

2.
Proc Natl Acad Sci U S A ; 118(41)2021 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-34615713

RESUMO

Electrification of chemical reactions is crucial to fundamentally transform our society that is still heavily dependent on fossil resources and unsustainable practices. In addition, electrochemistry-based approaches offer a unique way of catalyzing reactions by the fast and continuous alteration of applied potentials, unlike traditional thermal processes. Here, we show how the continuous cyclic application of electrode potential allows Pt nanoparticles to electrooxidize biomass-derived polyols with turnover frequency improved by orders of magnitude compared with the usual rates at fixed potential conditions. Moreover, secondary alcohol oxidation is enhanced, with a ketoses-to-aldoses ratio increased up to sixfold. The idea has been translated into the construction of a symmetric single-compartment system in a two-electrode configuration. Its operation via voltage cycling demonstrates high-rate sorbitol electrolysis with the formation of H2 as a desired coproduct at operating voltages below 1.4 V. The devised method presents a potential approach to using renewable electricity to drive chemical processes.

3.
Angew Chem Int Ed Engl ; 63(22): e202403466, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38451163

RESUMO

Tailoring the selectivity at the electrode-electrolyte interface is one of the greatest challenges for heterogeneous electrocatalysis, and complementary strategies to catalyst structural designs need to be developed. Herein, we proposed a new strategy of controlling the electrocatalytic pathways by lateral adsorbate interaction for the bio-polyol oxidation. Redox-innocent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) anion possesses the alcoholic property that facilely adsorbs on the nickel oxyhydroxide catalyst, but is resistant to oxidation due to the electron-withdrawing trifluoromethyl groups. The alien HFIP adsorbents can compete with bio-polyols and form a mixed adsorbate layer that creates lateral adsorbate interaction via hydrogen bonding, which achieved a >2-fold enhancement of the oxalate selectivity to 55 % for the representative glycerol oxidation and can be extended to various bio-polyol substrates. Through in situ spectroscopic analysis and DFT calculation on the glycerol oxidation, we reveal that the hydrogen-bonded adsorbate interaction can effectively tune the adsorption energies and tailor the oxidation capabilities toward the targeted products. This work offers an additional perspective of tuning electrocatalytic reactions via introducing redox-innocent adsorbates to create lateral adsorbate interactions.

4.
Hum Reprod ; 38(12): 2433-2446, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37877417

RESUMO

STUDY QUESTION: What is the influence of dietary interventions, namely the low fermentable oligo-, di-, mono-saccharides, and polyols (Low FODMAP) diet and endometriosis diet, on endometriosis-related pain and quality of life (QoL) compared to a control group? SUMMARY ANSWER: After adhering to a dietary intervention for 6 months, women with endometriosis reported less pain and an improved QoL compared to baseline whereas, compared to the control group, they reported less bloating and a better QoL in 3 of 11 domains. WHAT IS KNOWN ALREADY: Standard endometriosis treatment can be insufficient or may be accompanied by unacceptable side effects. This has resulted in an increasing interest in self-management strategies, including the appliance of the Low FODMAP diet and the endometriosis diet (an experience-based avoidance diet, developed by women with endometriosis). The Low FODMAP diet has previously been found effective in reducing endometriosis-related pain symptoms, whereas only limited studies are available on the efficacy of the endometriosis diet. A survey study recently found the endometriosis diet effective in improving QoL but currently no guidelines on use of the diet exist. STUDY DESIGN, SIZE, DURATION: A prospective one-center pilot study was performed between April 2021 and December 2022. Participants could choose between adherence to a diet-the Low FODMAP diet or endometriosis diet-or no diet (control group). Women adhering to a diet received extensive guidance from a dietician in training. The follow-up period was 6 months for all three groups. For all outcomes, women adhering to the diets were compared to their baseline situation and to the control group. PARTICIPANTS/MATERIALS, SETTING, METHODS: We included women diagnosed with endometriosis (surgically and/or by radiologic imaging) who reported pain scores ≥3 cm on the visual analogue score (0-10 cm) for dysmenorrhea, deep dyspareunia, and/or chronic pelvic pain. The primary endpoint focused on pain reduction for all pain symptoms, including dysuria, bloating, and tiredness. Secondary endpoints, assessed via questionnaires, focused on QoL, gastro-intestinal health, and diet adherence. MAIN RESULTS AND THE ROLE OF CHANCE: A total of 62 participants were included in the low FODMAP diet (n = 22), endometriosis diet (n = 21), and control group (n = 19). Compared to their baseline pain scores, participants adhering to a diet reported less pain in four of six symptoms (range P < 0.001 to P = 0.012) and better scores in 6 of 11 QoL domains (range P < 0.001 to P = 0.023) after 6 months. Compared to the control group, analyzed longitudinally over the 6-month follow-up period, participants applying a diet reported significant less bloating (P = 0.049), and better scores in 3 of 11 QoL domains (range P = 0.002 to P = 0.035). LIMITATIONS, REASONS FOR CAUTION: No sample size was calculated since efficacy data were lacking in the literature. In order to optimize dietary adherence, randomization was not applied, possibly resulting in selection bias. WIDER IMPLICATIONS OF THE FINDINGS: Our study suggests that women could benefit from adherence to a dietary intervention, since we found lower pain scores and better QoL after 6 months. However, caution is implied since this is a pilot study, no sample size was calculated, and data on long-term effects (>6 months) are lacking. The results of this pilot study underline the importance of further research and the drawing up of guidelines. STUDY FUNDING/COMPETING INTEREST(S): A.v.H. reports receiving a travel grant from Merck outside the scope of this study. J.W., S.V., J.T., and B.D.B. have no conflicts of interest to report. A.d.V. reports having received KP-register points for internship guidance of J.W., performing paid consultations with endometriosis patients outside the study and receiving reimbursements for educational lectures at the local hospital (Albert Schweitzer Ziekenhuis, Dordrecht, the Netherlands). A.S. reports having received expenses for travel and hotel costs as an invited speaker from ESHRE. This was outside the scope of this study. M.v.W. reports that she is a Co-Ed of Cochrane Gynecology and Fertility. V.M. reports receiving travel and speaker's fees from Guerbet and research grants from Guerbet, Merck and Ferring. The department of reproductive medicine (V.M.) of the Amsterdam UMC, location VUmc, has received several research and educational grants from Guerbet, Merck and Ferring not related to the submitted work. TRIAL REGISTRATION NUMBER: N/A.


Assuntos
Endometriose , Humanos , Feminino , Endometriose/complicações , Estudos Prospectivos , Qualidade de Vida , Grupos Controle , Projetos Piloto , Dor Pélvica/terapia , Dor Pélvica/complicações
5.
Int J Mol Sci ; 24(22)2023 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-38003653

RESUMO

This paper consists of a deep analysis and data comparison of the main strategies undertaken for achieving truly reversible capture of carbon dioxide involving optimized gas uptakes while affording weakest retention strength. So far, most strategies failed because the estimated amount of CO2 produced by equivalent energy was higher than that captured. A more viable and sustainable approach in the present context of a persistent fossil fuel-dependent economy should be based on a judicious compromise between effective CO2 capture with lowest energy for adsorbent regeneration. The most relevant example is that of so-called promising technologies based on amino adsorbents which unavoidably require thermal regeneration. In contrast, OH-functionalized adsorbents barely reach satisfactory CO2 uptakes but act as breathing surfaces affording easy gas release even under ambient conditions or in CO2-free atmospheres. Between these two opposite approaches, there should exist smart approaches to tailor CO2 retention strength even at the expense of the gas uptake. Among these, incorporation of zero-valent metal and/or OH-enriched amines or amine-enriched polyol species are probably the most promising. The main findings provided by the literature are herein deeply and systematically analysed for highlighting the main criteria that allow for designing ideal CO2 adsorbent properties.


Assuntos
Dióxido de Carbono , Gases , Aminas , Combustíveis Fósseis , Tecnologia
6.
Int J Mol Sci ; 24(3)2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36769079

RESUMO

Dry eye disease is among the most prevalent diseases affecting the ocular surface. Artificial tears remain the cornerstone therapy for its management. There are currently a wide variety of marketed artificial tears available to choose from. These artificial tears differ significantly in their composition and formulation. This article reviews the physicochemical and biological properties of artificial tear components and how these characteristics determine their use and efficacy in the management of dry eye. Furthermore, this article also discusses the various formulations of artificial tears such as macro and nanoemulsion and the type of preservatives present in them.


Assuntos
Síndromes do Olho Seco , Lubrificantes Oftálmicos , Humanos , Lubrificantes Oftálmicos/farmacologia , Lubrificantes Oftálmicos/uso terapêutico , Síndromes do Olho Seco/tratamento farmacológico , Veículos Farmacêuticos , Lágrimas , Soluções Oftálmicas/farmacologia , Soluções Oftálmicas/uso terapêutico
7.
Angew Chem Int Ed Engl ; 62(35): e202305186, 2023 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-37157011

RESUMO

Ultra-low molecular weight (ULMW) CO2 -polyols with well-defined hydroxyl end groups represent useful soft segments for the preparation of high-performance polyurethane foams. However, owing to the poor proton tolerance of catalysts towards CO2 /epoxide telomerization, it remains challenging to synthesize ULMW yet colorless CO2 -polyols. Herein, we propose an immobilization strategy of constructing supported catalysts by chemical anchoring of aluminum porphyrin on Merrifield resin. The resulting supported catalyst displays both extremely high proton tolerance (≈8000 times the equivalents of metal centers) and independence of cocatalyst, affording CO2 -polyols with ULMW (580 g mol-1 ) and high polymer selectivity (>99 %). Moreover, the ULMW CO2 -polyols with various architectures (tri-, quadra-, and hexa-arm) can be obtained, suggesting the wide proton universality of supported catalysts. Notably, benefiting from the heterogeneous nature of the supported catalyst, colorless products can be facilely achieved by simple filtration. The present strategy provides a platform for the synthesis of colorless ULMW polyols derived from not only CO2 /epoxides, but also lactone, anhydrides etc. or their combinations.

8.
J Biol Chem ; 297(1): 100806, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-34022223

RESUMO

Sensing noxiously high temperatures is crucial for living organisms to avoid heat-induced injury. The TRPV1 channel has long been known as a sensor for noxious heat. However, the mechanism of how this channel is activated by heat remains elusive. Here we found that a series of polyols including sucrose, sorbitol, and hyaluronan significantly elevate the heat activation threshold temperature of TRPV1. The modulatory effects of these polyols were only observed when they were perfused extracellularly. Interestingly, mutation of residues E601 and E649 in the outer pore region of TRPV1 largely abolished the effects of these polyols. We further observed that intraplantar injection of polyols into the hind paws of rats reduced their heat-induced pain response. Our observations not only suggest that the extracellular regions of TRPV1 are critical for the modulation of heat activation by polyols, but also indicate a potential role of polyols in reducing heat-induced pain sensation.


Assuntos
Temperatura Alta , Polímeros/farmacologia , Canais de Cátion TRPV/metabolismo , Sequência de Aminoácidos , Animais , Capsaicina/farmacologia , Espaço Extracelular/química , Feminino , Células HEK293 , Humanos , Ativação do Canal Iônico/efeitos dos fármacos , Polímeros/química , Prótons , Ratos Wistar , Canais de Cátion TRPV/química
9.
Curr Issues Mol Biol ; 44(11): 5531-5542, 2022 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-36354686

RESUMO

There is a problem of declining quality of rooster semen in the "native semen-equilibrium-short-term and long-term storage (cryopreservation)" cycle. The aim of this study was to determine the effects of various methods of preparing rooster semen on its qualitative characteristics, taking into account the method of removing possible contaminants (centrifugation or filtration), and to evaluate the change in the composition of the cytosol of the spermatozoon of the native semen, during equilibration of the diluted semen and during short-term storage. In this study, semen from roosters (n = 22) of the Russian White breed was used. Experiment 1: semen was divided into 3 aliquots: I-was diluted with synthetic cryoprotective medium (1:1 with LCM control, II-was filtered (membrane pore Ø 0.2 µm), and III-was centrifugated (at 3000 rpm for 10 min). Native and frozen/thawed semen was evaluated. Experiment 2: the composition of carbohydrates and polyols of the spermatozoa of native semen was evaluated during equilibration and after storage (3 h). The results of Experiment 1 showed an advantage in the quality of filtered semen compared to centrifuged in terms of progressive motility (41.0% vs. 27.0%) and chromatin integrity (56.6% vs. 33.6%). Results from frozen/thawed samples of filtered semen compared to centrifuged in terms of progressive motility were 25.5% vs. 5.5%, respectively, and in terms of chromatin integrity-83.5% vs. 64.4%, respectively. The results of Experiment 2 showed the main component in the composition of the native spermatozoa cytosol in assessing the content of carbohydrates and polyols was inositol-75.6%. The content of inositol decreased during storage by 6.5 times (from 0.030 mg/mL to 0.007 mg/mL), proposing the role of inositol as the main antioxidant in the cytosol of spermatozoa, which makes it biologically justified to introduce inositol into the composition of synthetic diluents, including cryoprotective ones.

10.
Planta ; 256(1): 13, 2022 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-35713726

RESUMO

MAIN CONCLUSION: Sorbitol metabolism plays multiple roles in many plants, including energy and carbon enrichment, effective defence against various stresses and other emerging specific roles. The underlying mechanisms are, however, incompletely understood. This review provides the current state-of-the-art, highlights missing knowledge and poses several remaining questions. The basic properties of sugar alcohols are summarised and pathways of sorbitol metabolism, including biosynthesis, degradation and key enzymes are described. Sorbitol transport within the plant body is discussed and individual roles of sorbitol in different organs, specific cells or even cellular compartments, are elaborated, clarifying the critical importance of sorbitol allocation and distribution. In addition to plants that accumulate and transport significant quantities of sorbitol (usual producers), there are some that synthesize small amounts of sorbitol or only possess sorbitol metabolising enzymes (non-usual producers). Modern analytical methods have recently enabled large amounts of data to be acquired on this topic, although numerous uncertainties and questions remain. For a long time, it has been clear that enriching carbohydrate metabolism with a sorbitol branch improves plant fitness under stress. Nevertheless, this is probably valid only when appropriate growth and defence trade-offs are ensured. Information on the ectopic expression of sorbitol metabolism genes has contributed substantially to our understanding of the sorbitol roles and raises new questions regarding sorbitol signalling potential. We finally examine strategies in plants producing sorbitol compared with those producing mannitol. Providing an in-depth understanding of sugar alcohol metabolism is essential for the progress in plant physiology as well as in targeted, knowledge-based crop breeding.


Assuntos
Sorbitol , Álcoois Açúcares , Metabolismo dos Carboidratos , Manitol/metabolismo , Álcoois Açúcares/metabolismo
11.
Clin Oral Investig ; 26(12): 7243-7252, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-35984512

RESUMO

OBJECTIVES: This in vitro study evaluated the efficacy of toothpaste containing fluoride (F), sodium trimetaphosphate (TMP), and xylitol and erythritol (XE) to inhibit or repair initial enamel erosion lesions. MATERIALS AND METHODS: Bovine enamel blocks (n = 120) were selected according to surface hardness (SH) and randomly divided into 5 experimental groups (n = 24 blocks/group): Placebo (no F, TMP, XE); 1100 ppm F; 16% xylitol + 4% erythritol (XE); 200 ppm F + 0.2% TMP (200 ppm F/TMP); and 200 ppm F + 0.2% TMP + 16% xylitol + 4% erythritol (200 ppm F/TMP/XE). The sound and softened blocks were immersed in toothpaste slurry in human saliva for 2 min. The blocks were then submitted to 4 erosive challenges in citric acid (0.75%, pH 3.5), each challenge for 1 min, with stirring. The SH of the blocks was determined after treatment (t) and after the 4 erosive challenges. In addition, the precipitates were analyzed by scanning electron microscopy (SEM). Variables were submitted to a two-way repeated-measures analysis of variance followed by a Student-Newman-Keuls test (p < 0.05). RESULTS: Toothpaste containing 200 ppm F/TMP/XE led to the highest protective and repair effect compared to the other groups (p < 0.001). The protective and repair effect was XE > 200 ppm F/TMP > 1100 ppm F > placebo (p < 0.001). All groups produced precipitates with a thicker layer for XE and TMP groups. CONCLUSIONS: Toothpaste containing 200 ppm F, TMP, and polyols demonstrated a superior protective and repair effect in initial enamel erosive lesions in vitro. CLINICAL RELEVANCE: Toothpaste containing F and polyols could be an advantage in patients affected by dental erosion, due to its higher preventive potential, mainly in individuals who frequently drink acidic beverages. However, future studies are needed to confirm these results.


Assuntos
Fluoretos , Cremes Dentais , Animais , Bovinos , Humanos , Cariostáticos/farmacologia , Esmalte Dentário , Eritritol/farmacologia , Fluoretos/análise , Dureza , Concentração de Íons de Hidrogênio , Fluoreto de Sódio/farmacologia , Cremes Dentais/farmacologia , Cremes Dentais/uso terapêutico , Xilitol/farmacologia
12.
Int J Mol Sci ; 23(12)2022 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-35743060

RESUMO

The operation of mechanical equipment inevitably generates vibrations and noise, which are harmful to not only the human body but also to the equipment in use. Damping materials, which can convert mechanical energy into thermal energy, possess excellent damping properties in the glass transition region and can alleviate the problems caused by vibration and noise. However, these materials mainly rely on petroleum-based resources, and their glass transition temperatures (Tg) are lower than room temperature. Therefore, bio-based materials with high damping properties at room temperature must be designed for sustainable development. Herein, we demonstrate the fabrication of bio-based millable polyurethane (BMPU)/hindered phenol composites that could overcome the challenges of sustainable development and exhibit high damping properties at room temperature. BMPUs with a high Tg were prepared from modified poly (lactic acid)-based polyols, the unsaturated chain extender trimethylolpropane diallylether, and 4,4'-diphenylmethane diisocyanate, and 3,9-Bis-{1,1-dimethyl-2[ß-(3-tert-butyl-4-hydroxy-5-methylphenyl-)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro [5,5]-undecane (AO-80) was added to prepare BMPU/AO-80 composites. Finally, the properties of the BMPUs and BMPU/AO-80 composites were systematically evaluated. After adding 30 phr of AO-80, the Tg and maximum loss factor (tan δmax) of BMPU/AO-80 composites increased from 7.8 °C to 13.5 °C and from 1.4 to 2.0, respectively. The tan δmax showed an improvement of 43%. Compared with other polyurethanes, the prepared BMPU/AO-80 composites exhibited higher damping properties at room temperature. This study proposes a new strategy to reduce society's current dependence on fossil resources and design materials featuring high damping properties from sustainable raw materials.


Assuntos
Poliuretanos , Temperatura
13.
Molecules ; 27(15)2022 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-35956835

RESUMO

To realize the commercialization of sustainable materials, new polymers must be generated and systematically evaluated for material characteristics and end-of-life treatment. Polyester polyols made from renewable monomers have found limited adoption in thermoplastic polyurethane (TPU) applications, and their broad adoption in manufacturing may be possible with a more detailed understanding of their structure and properties. To this end, we prepared a series of bio-based crystalline and amorphous polyester polyols utilizing azelaic acid and varying branched or non-branched diols. The prepared polyols showed viscosities in the range of 504-781 cP at 70 °C, with resulting TPUs that displayed excellent thermal and mechanical properties. TPUs prepared from crystalline azelate polyester polyol exhibited excellent mechanical properties compared to TPUs prepared from amorphous polyols. These were used to demonstrate prototype products, such as watch bands and cup-shaped forms. Importantly, the prepared TPUs had up to 85% bio-carbon content. Studies such as these will be important for the development of renewable materials that display mechanical properties suitable for commercially viable, sustainable products.


Assuntos
Ácidos Dicarboxílicos , Poliuretanos , Álcoois , Poliésteres , Poliuretanos/química
14.
Molecules ; 27(4)2022 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-35209165

RESUMO

In recent years, an increasing interest in reducing sugar consumption has been observed and many studies are conducted on the use of polyols in the osmotic dehydration process to obtain candied or dried fruits. The studies in the literature have focused on the kinetics of the process as well as the basic physical properties. In the scientific literature, there is a lack of investigation of the influence of such polyol solutions such as sorbitol and mannitol used as osmotic substances during the osmotic dehydration process on the contents of bioactive components, including natural colourants. Thus, the aim of the study was to evaluate the impact of polyols (mannitol and sorbitol) in different concentrations on the process kinetics and on chosen physical (colour and structural changes) as well as chemical (sugars and polyol content, total anthocyanin content, total polyphenol content, vitamin C, antioxidant activity) properties of osmotic-dehydrated organic strawberries. Generally, the results showed that the best solution for osmotic dehydration is 30% or 40% sorbitol solutions, while mannitol solution is not recommended due to difficulties with preparing a high-concentration solution and its crystallization in the tissue. In the case of sorbitol, the changes of bioactive compounds, as well as colour change, were similar to the sucrose solution. However, the profile of the sugar changed significantly, in which sucrose, glucose, and fructose were reduced in organic strawberries and were partially replaced by polyols.


Assuntos
Fragaria/química , Fragaria/efeitos dos fármacos , Frutas/química , Frutas/efeitos dos fármacos , Compostos Fitoquímicos/química , Compostos Fitoquímicos/farmacologia , Polímeros/farmacologia , Desidratação , Relação Dose-Resposta a Droga , Cinética , Osmose , Compostos Fitoquímicos/análise , Polifenóis/análise , Sacarose/análise
15.
Molecules ; 27(20)2022 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-36296482

RESUMO

Reactions of oxirane ring opening provide a powerful tool for regio- and stereoselective synthesis of polyfunctional and heterocyclic compounds, widely used in organic chemistry and drug design. Cyclooctane, alongside other medium-sized rings, is of interest as a novel molecular platform for the construction of target-oriented leads. Additionally, cyclooctane derivatives are well known to be prone to transannular reactions, which makes them a promising object in the search for novel approaches to polycyclic structures. In the present work, a series of cyclooctanediones was studied in Corey-Chaykovsky reactions, and novel spirocyclic bis(oxiranes) containing cyclooctane core, namely, 1,5-dioxadispiro[2.0.2.6]dodecane and 1,8-dioxadispiro[2.3.2.3]dodecane, were synthesized. Ring opening of the obtained bis(oxiranes) upon treatment with sodium azide was investigated, and it was found that the reaction path is determined by the reciprocal orientation of oxygen atoms in the oxirane moieties. Diastereomers of the bis(oxiranes) with cis-orientation underwent independent ring opening, supplying corresponding diazidodiols, while in the case of stereoisomers with trans-orientation, domino-like reactions occurred, including intramolecular nucleophilic attack and the formation of a novel three- or six-membered O-containing ring. Summarily, a straightforward approach to polyfunctional compounds containing cyclooctane or oxabicyclo[3.3.1]nonane cores, employing bis(oxiranes), was elaborated.


Assuntos
Compostos de Epóxi , Óxido de Etileno , Óxido de Etileno/química , Compostos de Epóxi/química , Azida Sódica , Ciclo-Octanos , Oxigênio
16.
Angew Chem Int Ed Engl ; 61(21): e202116059, 2022 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-35261133

RESUMO

Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single-atom Pt1 /hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1 /HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2 -C4 polyols to corresponding primary hydroxy acids. It is found that the Pt-(O-P) linkages with strong electron-withdrawing function of PO4 3- (Pt1 -OPO4 3- pair active site) not only realize the activation of the C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO4 3- -coordination effect provides electrostatic stabilization for single-atom Pt, ensuring the highly efficient catalysis of Pt1 /HAP for over 160 hours with superior leaching resistance.

17.
BMC Microbiol ; 21(1): 145, 2021 05 13.
Artigo em Inglês | MEDLINE | ID: mdl-33985431

RESUMO

BACKGROUND: Group B streptococci (GBS) are important neonatal bacterial pathogens that can cause severe invasive disease in the newborn. It is thought that in many cases of invasive neonatal GBS disease, the bacteria ascend the vagina into the uterus and infect the amniotic fluid surrounding the fetus. Important constituents of this environment include the polyols or sugar alcohols of which erythritol, sorbitol and mannitol are examples. The aim of our study was to investigate the effect of polyols on GBS grown in media containing these sugar alcohols. RESULTS: GBS incubated in varying concentrations of polyols (erythritol, sorbitol or mannitol) did not display any significant enhancement or inhibition of bacterial growth. However, growth of GBS in the presence of erythritol significantly increased the surface expression of GBS-PGK (a plasminogen binding protein) 1.25 to 1.5-fold depending on the erythritol concentration and significantly enhanced the survival in human blood 3X to 18X depending on the concentration of polyol used. Interestingly, GBS grown in 1% erythritol significantly increased invasion by the bacteria of HeLa cells (epithelial cell line) (150% vs 100%) however, at higher concentrations (2% or 4% of polyol) the number of CFUs was significantly reduced (55-75% vs 100%) suggesting higher concentrations of polyols may inhibit invasion. Erythritol also increased GBS hemolytic activity as well as enhancing biofilm formation 1.4X to 3.3X depending on the concentration of polyol used. CONCLUSIONS: GBS grown in the presence of polyols alters the bacteria's phenotype resulting in changes associated with GBS virulence. This effect was greatest for the polyol erythritol.


Assuntos
Eritritol/metabolismo , Manitol/metabolismo , Polímeros/metabolismo , Sorbitol/metabolismo , Streptococcus agalactiae/crescimento & desenvolvimento , Células HeLa , Humanos , Fenótipo , Infecções Estreptocócicas/microbiologia , Streptococcus agalactiae/metabolismo , Streptococcus agalactiae/patogenicidade , Virulência
18.
Microb Cell Fact ; 20(1): 195, 2021 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-34627248

RESUMO

BACKGROUND: Contemporary biotechnology focuses on many problems related to the functioning of developed societies. Many of these problems are related to health, especially with the rapidly rising numbers of people suffering from civilization diseases, such as obesity or diabetes. One factor contributing to the development of these diseases is the high consumption of sucrose. A very promising substitute for this sugar has emerged: the polyhydroxy alcohols, characterized by low caloric value and sufficient sweetness to replace table sugar in food production. RESULTS: In the current study, yeast belonging to the Yarrowia clade were tested for erythritol, mannitol and arabitol production using crude glycerol from the biodiesel and soap industries as carbon sources. Out of the 13 tested species, Yarrowia divulgata and Candida oslonensis turned out to be particularly efficient polyol producers. Both species produced large amounts of these compounds from both soap-derived glycerol (59.8-62.7 g dm-3) and biodiesel-derived glycerol (76.8-79.5 g dm-3). However, it is equally important that the protein and lipid content of the biomass (around 30% protein and 12% lipid) obtained after the processes is high enough to use this yeast in the production of animal feed. CONCLUSIONS: The use of waste glycerol for the production of polyols as well as utilization of the biomass obtained after the process for the production of feed are part of the development of modern waste-free technologies.


Assuntos
Biocombustíveis/microbiologia , Biotecnologia/métodos , Polímeros/isolamento & purificação , Saccharomycetales/metabolismo
19.
J Therm Biol ; 98: 102950, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-34016367

RESUMO

The Russian wheat aphid Diuraphis noxia (Kurdjumov) and melon aphid Aphis gossypii Glover are known as winter and summer active species, respectively. It is hypothesized that differences in the aphids' seasonal activities might be related to their response to temperature extremes and different physiological mechanisms. To study the aphids' thermal tolerance variations and mode of their physiological basis, they were cold acclimated at 20, 15, 10, 5, and 0 °C for 168 h (7 days) and heat acclimated at 20, 25, 30 °C for 168 h and 35 °C for 48 h. At the end of each thermal regime, survival at low and high temperatures was determined, and changes in sugars and polyols and heat shock protein 70 (Hsp70) were investigated. D. noxia was more cold-tolerant, while A. gossypii was a more heat-tolerant insect. The type and pattern of sugars and polyols were similar in both species under cold acclimation (ACC) and heat acclimation (HCC). In both species, glucose and mannitol were the major identified compounds involved in cold and heat tolerance. However, they showed different patterns of Hsp70 level, with D. noxia having a higher level of Hsp70 under ACC and A. gossypii having a higher level of Hsp70 under HCC. These results demonstrated that their differences in thermal tolerance might explain the seasonal activities of the aphids.


Assuntos
Afídeos/fisiologia , Termotolerância , Animais , Afídeos/metabolismo , Temperatura Baixa , Glucose/metabolismo , Proteínas de Choque Térmico HSP70/metabolismo , Temperatura Alta , Proteínas de Insetos/metabolismo , Manitol/metabolismo , Polímeros/metabolismo , Estações do Ano , Trealose/metabolismo
20.
Int J Mol Sci ; 22(2)2021 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-33419222

RESUMO

One of the consequences of climate change is the expansion of insects' ranges. Colonization of new habitats forces insects to adapt to new conditions, such as low temperatures in winter. Cinara tujafilina is a thermophilic anholocyclic aphid species, which reproduce exclusively parthenogenetic throughout the year, including winter. On the areas where the populations of C. tujafilina had expanded, it demonstrated its adaptation for surviving colder winters. Based on analyses of changes in body chemical composition using Fourier transform infrared (FTIR) and changes in cryoprotectant content using high performance liquid chromatography (HPLC), we showed how aphid C. tujafilina adapted to overwintering as an active stage. In the FTIR spectrum of the winter type of C. tujafilina, higher peak values originating from the carbohydrates, proteins and lipids, were observed. Glucose, trehalose, mannitol, myo-inositol and glycerol were identified in the aphid body in winter as main putative cryoprotectants to increase the insects' tolerance to cold. The complex sugar-polyol cryoprotectant system facilitates aphids' survival in unfavorable low temperatures.


Assuntos
Adaptação Fisiológica , Afídeos/metabolismo , Temperatura Baixa , Crioprotetores/metabolismo , Estações do Ano , Animais , Cromatografia Líquida de Alta Pressão/métodos , Mudança Climática , Ecossistema , Glucose/metabolismo , Insetos/metabolismo , Larva/metabolismo , Manitol/metabolismo , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Trealose/metabolismo
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