ABSTRACT: A unique class of aromatic ether polymers
containing perfluorocyclopentenyl (PFCP) enchainment was
prepared from the simple step growth polycondensation of
commercial bisphenols and octafluorocyclopentene (OFCP)
in the presence of triethylamine. Model studies indicate that
the second addition/elimination on OFCP is fast and poly-
condensation results in linear homopolymers and copolymers
without side products. The synthesis of bis(heptafluoro-
cyclopentenyl) aryl ether monomers and their condensation
with bisphenols further led to PFCP copolymers with alternating structures. This new class of semifluorinated polymers exhibit surprisingly high crystallinity in some cases and excellent thermal stability.
Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catal...Pawan Kumar
Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on polyaniline
support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols to the corresponding
carbonyl compounds in high to excellent yield using molecular oxygen as oxidant and isobutyraldehyde
as a sacrificial agent. Notably, the synthesized catalyst was found to be truly heterogeneous in nature and
could be easily recovered, recycled for several recycling runs without loss of catalytic activity
Bis-perfluorocycloalkenyl (PFCA) aryl ether monomers towards a versatile clas...Babloo Sharma, Ph.D.
A unique class of perfluorocycloalkenyl (PFCA) aryl ether monomers was synthesized from commercially available perfluorocycloalkenes (PFCAs) and bisphenols in good yields. This facile one pot reaction of perfluorocycloalkenes, namely, octafluorocyclopentene (OFCP), and decafluorocyclohexene (DFCH), with bisphenols occurs at room temperature via an addition–elimination reaction in the presence of a base. The synthesis of PFCA monomers and their condensation with bisphenols lead to perfluorocycloalkenyl (PFCA) aryl ether homopolymers and copolymers with random and/or alternating polymer architectures.
Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catal...Pawan Kumar
Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on polyaniline
support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols to the corresponding
carbonyl compounds in high to excellent yield using molecular oxygen as oxidant and isobutyraldehyde
as a sacrificial agent. Notably, the synthesized catalyst was found to be truly heterogeneous in nature and
could be easily recovered, recycled for several recycling runs without loss of catalytic activity
Bis-perfluorocycloalkenyl (PFCA) aryl ether monomers towards a versatile clas...Babloo Sharma, Ph.D.
A unique class of perfluorocycloalkenyl (PFCA) aryl ether monomers was synthesized from commercially available perfluorocycloalkenes (PFCAs) and bisphenols in good yields. This facile one pot reaction of perfluorocycloalkenes, namely, octafluorocyclopentene (OFCP), and decafluorocyclohexene (DFCH), with bisphenols occurs at room temperature via an addition–elimination reaction in the presence of a base. The synthesis of PFCA monomers and their condensation with bisphenols lead to perfluorocycloalkenyl (PFCA) aryl ether homopolymers and copolymers with random and/or alternating polymer architectures.
Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catal...Pawan Kumar
Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on
polyaniline support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols
to the corresponding carbonyl compounds in high to excellent yield using molecular oxygen as
oxidant and isobutyraldehyde as a sacrificial agent. Notably, the synthesized catalyst was found
to be truly heterogeneous in nature and could be easily recovered, recycled for several recycling
runs without loss of catalytic activity
Perfluorocyclohexenyl Aryl Ether Polymers via Polycondensation of Decafluoroc...aaaa zzzz
ABSTRACT: A novel class of semifluorinated perfluorocyclohex- enyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step-growth polymer- ization of commercially available bisphenols and decafluorocy- clohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis-perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal
stabilities with a 5% decomposition temperature ranging from 359 to 444 ﰀC in air and nitrogen atmosphere. These semifluori- nated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as cross- linking and application specific functionalization possible. VC 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 232–238
Computer-assisted study on the reaction between pyruvate and ylide in the pat...Omar Alvarardo
n this study the formation of the lactyl–thia-
min diphosphate intermediate (L–ThDP) is addressed using
density functional theory calculations at X3LYP/6-
31??G(d,p) level of theory. The study includes potential
energy surface scans, transition state search, and intrinsic
reaction coordinate calculations. Reactivity is analyzed in
terms of Fukui functions. The results allow to conclude that
the reaction leading to the formation of L–ThDP occurs via
a concerted mechanism, and during the nucleophilic attack
on the pyruvate molecule, the ylide is in its AP form. The
calculated activation barrier for the reaction is 19.2 kcal/
mol, in agreement with the experimental reported value.
Introduction of poly-cyclic compounds, resonance, molecular orbital structure, physical properties, preparation, reaction and uses of napthalene, anthracene, phenanthrene, napthaquinone, napthol, napthylamine, 9,10 anthraquinone and phenanthrequinone.
Basic principles & questions and answers of organic chemistry Bryar Ali Rus
this is some basic principles and question & answers of previous years of organic chemistry with notes on dr.emad manhal's examination , school of pharmacy , university of sulaimani .
Prof Tom Reardon's talk from the Australian Agricultural & Resource Economics Society's event "Reframing the Food Agenda: Setting the Scene for Australia" held August 19, 2011
Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catal...Pawan Kumar
Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on
polyaniline support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols
to the corresponding carbonyl compounds in high to excellent yield using molecular oxygen as
oxidant and isobutyraldehyde as a sacrificial agent. Notably, the synthesized catalyst was found
to be truly heterogeneous in nature and could be easily recovered, recycled for several recycling
runs without loss of catalytic activity
Perfluorocyclohexenyl Aryl Ether Polymers via Polycondensation of Decafluoroc...aaaa zzzz
ABSTRACT: A novel class of semifluorinated perfluorocyclohex- enyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step-growth polymer- ization of commercially available bisphenols and decafluorocy- clohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis-perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal
stabilities with a 5% decomposition temperature ranging from 359 to 444 ﰀC in air and nitrogen atmosphere. These semifluori- nated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as cross- linking and application specific functionalization possible. VC 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 232–238
Computer-assisted study on the reaction between pyruvate and ylide in the pat...Omar Alvarardo
n this study the formation of the lactyl–thia-
min diphosphate intermediate (L–ThDP) is addressed using
density functional theory calculations at X3LYP/6-
31??G(d,p) level of theory. The study includes potential
energy surface scans, transition state search, and intrinsic
reaction coordinate calculations. Reactivity is analyzed in
terms of Fukui functions. The results allow to conclude that
the reaction leading to the formation of L–ThDP occurs via
a concerted mechanism, and during the nucleophilic attack
on the pyruvate molecule, the ylide is in its AP form. The
calculated activation barrier for the reaction is 19.2 kcal/
mol, in agreement with the experimental reported value.
Introduction of poly-cyclic compounds, resonance, molecular orbital structure, physical properties, preparation, reaction and uses of napthalene, anthracene, phenanthrene, napthaquinone, napthol, napthylamine, 9,10 anthraquinone and phenanthrequinone.
Basic principles & questions and answers of organic chemistry Bryar Ali Rus
this is some basic principles and question & answers of previous years of organic chemistry with notes on dr.emad manhal's examination , school of pharmacy , university of sulaimani .
Prof Tom Reardon's talk from the Australian Agricultural & Resource Economics Society's event "Reframing the Food Agenda: Setting the Scene for Australia" held August 19, 2011
The determination of complex underlying relationships between system parameters from simulated and/or recorded data requires advanced interpolating functions, also known as surrogates. The development of surrogates for such complex relationships often requires the modeling of high dimensional and non-smooth functions using limited information. To this end, the hybrid surrogate modeling paradigm, where different surrogate models are aggregated, offers a robust solution. In this paper, we develop a new high fidelity surro- gate modeling technique that we call the Reliability Based Hybrid Functions (RBHF). The RBHF formulates a reliable Crowding Distance-Based Trust Region (CD-TR), and adap- tively combines the favorable characteristics of different surrogate models. The weight of each contributing surrogate model is determined based on the local reliability measure for that surrogate model in the pertinent trust region. Such an approach is intended to ex- ploit the advantages of each component surrogate. This approach seeks to simultaneously capture the global trend of the function and the local deviations. In this paper, the RBHF integrates four component surrogate models: (i) the Quadratic Response Surface Model (QRSM), (ii) the Radial Basis Functions (RBF), (iii) the Extended Radial Basis Functions (E-RBF), and (iv) the Kriging model. The RBHF is applied to standard test problems. Subsequent evaluations of the Root Mean Squared Error (RMSE) and the Maximum Ab- solute Error (MAE), illustrate the promising potential of this hybrid surrogate modeling approach.
This paper presents a new method (the Unrestricted Wind Farm Layout Optimization (UWFLO)) of arranging turbines in a wind farm to achieve maximum farm efficiency. The powers generated by individual turbines in a wind farm are dependent on each other, due to velocity deficits created by the wake effect. A standard analytical wake model has been used to account for the mutual influences of the turbines in a wind farm. A variable induction factor, dependent on the approaching wind velocity, estimates the velocity deficit across each turbine. Optimization is performed using a constrained Particle Swarm Optimization (PSO) algorithm. The model is validated against experimental data from a wind tunnel experiment on a scaled down wind farm. Reasonable agreement between the model and experimental results is obtained. A preliminary wind farm cost analysis is also performed to explore the effect of using turbines with different rotor diameters on the total power generation. The use of differing rotor diameters is observed to play an important role in improving the overall efficiency of a wind farm.
Bis-perfluorocycloalkenyl (PFCA) aryl ether monomers towards a versatile clas...aaaa zzzz
A unique class of perfluorocycloalkenyl (PFCA) aryl ether monomers was synthesized from commercially available perfluorocycloalkenes (PFCAs) and bisphenols in good yields. This facile one pot reaction of per- fluorocycloalkenes, namely, octafluorocyclopentene (OFCP), and decafluorocyclohexene (DFCH), with bisphenols occurs at room temperature via an addition–elimination reaction in the presence of a base. The synthesis of PFCA monomers and their condensation with bisphenols lead to perfluorocycloalkenyl (PFCA) aryl ether homopolymers and copolymers with random and/or alternating polymer architectures.
Published by Elsevier Ltd.
Poster Presentation and APL Materials Poster AwardKatja Kretschmer
Poster presented and Poster Award at the 5th Australia-China Conference on Science, Technology and Education and the 5th Australia-China Symposium for Material Science (July 2015)
Mechanistic Aspects of Oxidation of P-Bromoacetophen one by Hexacyanoferrate ...IJERA Editor
The kinetics of oxidation of p-bromoacetophenone by hexacyanoferrate (III) has been studied in alkaline
medium. The order of reaction with respect of both acetophenone and hexacynoferrate (III) has been found to be
unity. The rate of reaction increases with increase in the concentration of sodium hydroxide.On addition of
neutral KCl, reaction rate increases. The effects of solvent and temperature have been also studied. The product
p-bromophenyl glyoxal have been characterized by IR studies.
Reaction of aniline with ammonium persulphate and concentrated hydrochloric a...Maciej Przybyłek
In this paper, the reaction of aniline with ammonium persulphate and concentrated HCl was studied. As a result of our experimental studies, 2,4,6-trichlorophenylamine was identified as the main product. This shows that a high concentration of HCl does not favour oxidative polymerisation of phenylamine, even though the ammonium persulphate/HCl system is widely used in polyaniline synthesis. On the basis of the experimental data and density functional theory for reaction path modelling, we proposed a mechanism for oxidative chlorination of aniline. We assumed that this reaction proceeded in three cyclically repeated steps; protonation of aniline, formation of singlet ground state phenylnitrenium cation, and nucleophilic substitution. In order to confirm this mechanism, kinetic, thermochemical, and natural bond orbital population analyses were performed.
A variety of perfluorocycloalkenyl (PFCA) aryl ether monomers and polymers with enchained triarylamine units were successfully synthesized, characterized and reported here. These polymers are highly thermally stable and show variable thermal properties. Successful conver- sion of the newly synthesized TAA enchained perfluoro- cyclopentenyl (PFCP) aryl ether polymers via formylation and EAS demonstrates the synthetic versatility of TAA moiety and provides an excellent option for application specific post polymerization reactions. The cross-linking behavior of PFCP aryl ether polymers was studied under different reaction conditions. The combination of pro- cessability, thermal stabilities, and tailorability makes these polymers suitable for a wide variety of applications including electro-optics, proton exchange membranes and super-hydrophobic applications.
synthesis and spectral studies on cardanol based polyurethanesINFOGAIN PUBLICATION
Cardanol is a renewable organic resource obtained as a byproduct from the cashew industry. The present study has been carried out with an aim to manufacture rigid polyurethanes from natural and eco – friendly sources due to the rising prices of petrochemicals and also as an environmental concern. Vegetable oil based polyurethanes promising a new generation polymers which are low cost materials in the family of polyurethanes. Cardanol based phenolic resin has been synthesized by condensing cardanol with furfural in a particular mole ratio using phthalic acid as catalyst. The progress of the reaction was monitored by determining the free furfural and free phenol content. The resin was cured by using the curing agent 4, 41 - methylene bis(cyclohexyl isocyanate) and the catalyst dibutyltin dilaurate to produce polyurethane. Polyurethanes are an important class of polymers that have found place in many applications. The physico chemical and spectral properties of resin and polyurethane have also been studied.
Experimental and theoretical studies on the photodegradation of 2-ethylhexyl ...Maciej Przybyłek
2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H2O2, H2O2/HCl, H2O2/UV, and H2O2/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic acid (4-MCA), 4-methoxybenzaldehyde (4-MBA) and 4-methoxyphenol (4-MP) were identified. Experimental studies were enriched with DFT and MP2 calculations. We found that reactions of 4-MCA, 4-MBA and 4-MP with Cl2 and HOCl were in all cases thermodynamically favorable. However, reactivity indices provide a better explanation of the formation of particular chloroorganic compounds. Generally, those isomeric forms of mono- and dichlorinated compounds which exhibits the highest hardness were identified. Nucleophilicity of the chloroorganic compounds precursors were examined by means of the Fukui function.
A variety of perfluorocycloalkenyl (PFCA) arylether monomers and polymers with enchained triarylamineunits were successfully synthesized, characterized andreported here. These polymers are highly thermally stableand show variable thermal properties. Successful conver-sion of the newly synthesized TAA enchained perfluoro-cyclopentenyl (PFCP) aryl ether polymers via formylationand EAS demonstrates the synthetic versatility of TAAmoiety and provides an excellent option for applicationspecific post polymerization reactions. The cross-linkingbehavior of PFCP aryl ether polymers was studied underdifferent reaction conditions. The combination of pro-cessability, thermal stabilities, and tailorability makes thesepolymers suitable for a wide variety of applicationsincluding electro-optics, proton exchange membranes andsuper-hydrophobic applications.
Asymmetric Multipole Plasmon-Mediated Catalysis Shifts the Product Selectivit...Pawan Kumar
Cu/TiO2 is a well-known photocatalyst for the photocatalytic transformation of CO2 into methane. The formation of C2+ products such as ethane and ethanol rather than methane is more interesting due to their higher energy density and economic value, but the formation of C–C bonds is currently a major challenge in CO2 photoreduction. In this context, we report the dominant formation of a C2 product, namely, ethane, from the gas-phase photoreduction of CO2 using TiO2 nanotube arrays (TNTAs) decorated with large-sized (80–200 nm) Ag and Cu nanoparticles without the use of a sacrificial agent or hole scavenger. Isotope-labeled mass spectrometry was used to verify the origin and identity of the reaction products. Under 2 h AM1.5G 1-sun illumination, the total rate of hydrocarbon production (methane + ethane) was highest for AgCu-TNTA with a total CxH2x+2 rate of 23.88 μmol g–1 h–1. Under identical conditions, the CxH2x+2 production rates for Ag-TNTA and Cu-TNTA were 6.54 and 1.39 μmol g–1 h–1, respectively. The ethane selectivity was the highest for AgCu-TNTA with 60.7%, while the ethane selectivity was found to be 15.9 and 10% for the Ag-TNTA and Cu-TNTA, respectively. Adjacent adsorption sites in our photocatalyst develop an asymmetric charge distribution due to quadrupole resonances in large metal nanoparticles and multipole resonances in Ag–Cu heterodimers. Such an asymmetric charge distribution decreases adsorbate–adsorbate repulsion and facilitates C–C coupling of reaction intermediates, which otherwise occurs poorly in TNTAs decorated with small metal nanoparticles.
Alkali P-Nitrophenolates for Short Wavelength Laser GenerationEditor IJCATR
Single crystals of alkali p-Nitrophenolates namely sodium p-nitrophenolate dihydrate (SPNP), potassium p- nitrophenolate
monohydrate (PPNP) and lithium p-nitrophenolate trihydrate (LPNP) using Group I elements (Na, K, Li) and p-nitrophenols were grown
by solvent evaporation method. Single crystal XRD analysis shows that SPNP and LPNP crystallize in noncentrosymmetric space group
while PPNP is centrosymmetric. Using Autox software, all the peaks in the recorded powder XRD spectrum of the samples were identified
and indexed. The FT – IR spectra of the sample reveals the characteristic vibrations of the functional groups present in alkalinitrophenolates.
A weak absorption band around the region 1589–1641 cm-1 confirms the presence of the phenolic ring. A broad
intermolecular hydrogen bonded OH stretching at 3325 cm-1 of p- nitrophenol is shifted which shows the increase in the polarizable nature
of p–nitrophenol and thus easily forms a metal (sodium/ potassium/ lithium) coordination compound. UV-Vis spectrum shows that all the
crystals are transparent above 400 nm and has a wide optical window in the visible region. Intense absorption peak in the UV region may
be due to the colored nature of the compound. Addition of metal ion (sodium/potassium) modifies the optical transparency of the original
molecule (p-nitro phenol) and consequently introduces a bath chromic shift of 90/40 nm in the crystal transparency of the samples. Kurtz
powder technique result shows that the relative SHG efficiency of SPNP and LPNP was nearly 5 and 9.25 times of KDP.
This book focuses on novel perflurocycloalkenyl (PFCA) aryl ether polymers, derived via polycondensation of perfluorocycloalkenes with bisphenols. Chapter 1 describes the detailed background of fluorine, its reactivity and effect in organic chemistry. This chapter also discusses the application of fluoropolymers with a detailed study of two fluoropolymers: perfluorocyclobutyl aryl ether polymers and fluorinated arylene vinylene ether polymers. Chapter 2, 3 and 4 describe the detailed synthesis, characterization and different properties of bis-PFCA aryl ether monomers, perfluorocyclopentenyl (PFCP) aryl ether polymers and perfluorocyclohexenyl (PFCH) aryl ether polymers, respectively. Chapter 3 also includes the potential crosslinking and post-functionalization studies of PFCA aryl ether polymers. Chapter 5 discusses the application section of these newly synthesized PFCA aryl ether polymers. Ultra low dielectric constant (k = 1.53) materials with self-cleansing properties were synthesized via incorporation of fluorodecyl-polyhedral oligomeric silsesquioxane (FD-POSS) into PFCP aryl ether polymers.
Sulfonated perfluorocyclopentenyl polymers and uses thereofaaaa zzzz
An aspect of the invention is directed to a polymer comprising a Sulfonated PerfluorocycIopentyl compound. Another aspect of the invention is directed to a sulfonated copolymer comprising one or more sulfonated polymers.A further aspect of the invention is directed to membranes prepared from the polymers of the claimed invention.
Ultra low dielectric constant (k 1⁄4 1.53) materials with self-cleansing properties were synthesized via incorporation of fluorodecyl-polyhedral oligomeric silsesquioxane (FD-POSS) into recently synthesized perfluorocyclopentenyl (PFCP) aryl ether polymers. Incorporation of fluorine rich, high free volume, and low surface energy POSS into a semifluorinated PFCP polymer matrix at various weight percentages resulted in a dramatic drop in dielectric constant, as well as a significant increase in hydrophobicity and oleophobicity of the system. These ultra-low dielectric self-cleansing materials (qtilt 1⁄4 38) were fabricated into electrospun mats from a solvent blend of fluorinated FD-POSS with PFCP polymers.
Deep Behavioral Phenotyping in Systems Neuroscience for Functional Atlasing a...Ana Luísa Pinho
Functional Magnetic Resonance Imaging (fMRI) provides means to characterize brain activations in response to behavior. However, cognitive neuroscience has been limited to group-level effects referring to the performance of specific tasks. To obtain the functional profile of elementary cognitive mechanisms, the combination of brain responses to many tasks is required. Yet, to date, both structural atlases and parcellation-based activations do not fully account for cognitive function and still present several limitations. Further, they do not adapt overall to individual characteristics. In this talk, I will give an account of deep-behavioral phenotyping strategies, namely data-driven methods in large task-fMRI datasets, to optimize functional brain-data collection and improve inference of effects-of-interest related to mental processes. Key to this approach is the employment of fast multi-functional paradigms rich on features that can be well parametrized and, consequently, facilitate the creation of psycho-physiological constructs to be modelled with imaging data. Particular emphasis will be given to music stimuli when studying high-order cognitive mechanisms, due to their ecological nature and quality to enable complex behavior compounded by discrete entities. I will also discuss how deep-behavioral phenotyping and individualized models applied to neuroimaging data can better account for the subject-specific organization of domain-general cognitive systems in the human brain. Finally, the accumulation of functional brain signatures brings the possibility to clarify relationships among tasks and create a univocal link between brain systems and mental functions through: (1) the development of ontologies proposing an organization of cognitive processes; and (2) brain-network taxonomies describing functional specialization. To this end, tools to improve commensurability in cognitive science are necessary, such as public repositories, ontology-based platforms and automated meta-analysis tools. I will thus discuss some brain-atlasing resources currently under development, and their applicability in cognitive as well as clinical neuroscience.
Nutraceutical market, scope and growth: Herbal drug technologyLokesh Patil
As consumer awareness of health and wellness rises, the nutraceutical market—which includes goods like functional meals, drinks, and dietary supplements that provide health advantages beyond basic nutrition—is growing significantly. As healthcare expenses rise, the population ages, and people want natural and preventative health solutions more and more, this industry is increasing quickly. Further driving market expansion are product formulation innovations and the use of cutting-edge technology for customized nutrition. With its worldwide reach, the nutraceutical industry is expected to keep growing and provide significant chances for research and investment in a number of categories, including vitamins, minerals, probiotics, and herbal supplements.
(May 29th, 2024) Advancements in Intravital Microscopy- Insights for Preclini...Scintica Instrumentation
Intravital microscopy (IVM) is a powerful tool utilized to study cellular behavior over time and space in vivo. Much of our understanding of cell biology has been accomplished using various in vitro and ex vivo methods; however, these studies do not necessarily reflect the natural dynamics of biological processes. Unlike traditional cell culture or fixed tissue imaging, IVM allows for the ultra-fast high-resolution imaging of cellular processes over time and space and were studied in its natural environment. Real-time visualization of biological processes in the context of an intact organism helps maintain physiological relevance and provide insights into the progression of disease, response to treatments or developmental processes.
In this webinar we give an overview of advanced applications of the IVM system in preclinical research. IVIM technology is a provider of all-in-one intravital microscopy systems and solutions optimized for in vivo imaging of live animal models at sub-micron resolution. The system’s unique features and user-friendly software enables researchers to probe fast dynamic biological processes such as immune cell tracking, cell-cell interaction as well as vascularization and tumor metastasis with exceptional detail. This webinar will also give an overview of IVM being utilized in drug development, offering a view into the intricate interaction between drugs/nanoparticles and tissues in vivo and allows for the evaluation of therapeutic intervention in a variety of tissues and organs. This interdisciplinary collaboration continues to drive the advancements of novel therapeutic strategies.
Comparing Evolved Extractive Text Summary Scores of Bidirectional Encoder Rep...University of Maribor
Slides from:
11th International Conference on Electrical, Electronics and Computer Engineering (IcETRAN), Niš, 3-6 June 2024
Track: Artificial Intelligence
https://www.etran.rs/2024/en/home-english/
Richard's entangled aventures in wonderlandRichard Gill
Since the loophole-free Bell experiments of 2020 and the Nobel prizes in physics of 2022, critics of Bell's work have retreated to the fortress of super-determinism. Now, super-determinism is a derogatory word - it just means "determinism". Palmer, Hance and Hossenfelder argue that quantum mechanics and determinism are not incompatible, using a sophisticated mathematical construction based on a subtle thinning of allowed states and measurements in quantum mechanics, such that what is left appears to make Bell's argument fail, without altering the empirical predictions of quantum mechanics. I think however that it is a smoke screen, and the slogan "lost in math" comes to my mind. I will discuss some other recent disproofs of Bell's theorem using the language of causality based on causal graphs. Causal thinking is also central to law and justice. I will mention surprising connections to my work on serial killer nurse cases, in particular the Dutch case of Lucia de Berk and the current UK case of Lucy Letby.
This pdf is about the Schizophrenia.
For more details visit on YouTube; @SELF-EXPLANATORY;
https://www.youtube.com/channel/UCAiarMZDNhe1A3Rnpr_WkzA/videos
Thanks...!
Professional air quality monitoring systems provide immediate, on-site data for analysis, compliance, and decision-making.
Monitor common gases, weather parameters, particulates.
2. polymers containing fluorinated vinyl groups are found to be
potentially reactive and thermally cross-linkable.
Octafluorocyclopentene (OFCP) is a readily available
perfluorocyclic olefin with unique chemistry. Many studies
have been reported on the reaction of OFCP with nucleophiles,
such as phenoxides,12−15
arenethiolates,16
amines,17−19
eno-
lates, phosphonium ylides,20
and organolithium reagents.20−22
Many other examples include OFCP derivatives for photo-
chromic applications.23−25
There are very few examples of
polymers of perfluorocyclopentene by traditional chain growth
mechanisms. This perfluorocyclic olefin does not homopoly-
merize under radical conditions,26
and radical copolymeriza-
tions with styrene and vinyl acetate lead to copolymers with a
very low molar ratio of perfluorocyclopentene.27
Nevertheless,
copolymerization with electron-rich monomers like vinyl ethers
leads to alternating copolymers.26,27
Step growth polymer-
ization of OFCP with bis(silyl) ethers was reported, but the
resulting polymers exhibited low molecular weight.28
To our
knowledge, the polycondensation of bisphenols with perfluoro-
cycloolefins has not been previously reported.
■ RESULTS AND DISCUSSION
Prior to polycondensation, a model reaction was performed
using OFCP and sodium phenoxide (Scheme 3). Interestingly,
75% of the clean product mixture was the bis adduct as
determined by 19
F NMR spectroscopy, most likely due to
increased solubility of the monoadduct (Figure 1).
Polycondensation was attempted using the sodium salt of
bis(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF)
and OFCP in DMF at 80 °C for 10 h. Low-molecular-weight
oligomers were obtained. Thus, an alternative method was
explored using triethylamine as the base (Scheme 1) to afford
perfluorocyclopentenyl (PFCP) aryl ether homopolymer P1 of
number-average molecular weight and PDI of 9100 g mol−1
and
2.5, respectively (Table 1).
Moreover, homopolymer P1 was determined to be
hydroxytelechelic by the absence of 19
F NMR signals centered
at −149 ppm representative of the fluoroolefin (Figure 2b).
In the 1
H NMR spectrum (Figure 2a), there are two signals
representing aromatic (6.9 and 7.3 ppm) protons, as expected.
These signals (dd, J = 8.8 Hz) indicate a symmetric environ-
ment around both ether linkages of the PFCP rings and
support an addition−elimination reaction which leaves the
double bond of the PFCP ring intact. Further, 19
F NMR shows
three clean signals, corresponding to three unique fluorine
atoms in symmetrical environments, as expected (Figure 2b). A
PFCP end-capped polymer was also prepared by the addition
of an excess of OFCP at the end of the reaction.
PFCP aryl ether homopolymer P2 was prepared from
Bisphenol A via the same methodology as P1 (Scheme 1). For
homopolymer P2, the number-average molecular weight and
PDI were 9600 and 1.15 after 24 h reaction time (Table 1).
Homopolymer P2 was characterized by 1
H NMR and
19
F NMR spectroscopy and, as before, exhibited a clean
addition−elimination polycondensation (Figure 3). 1
H NMR
shows symmetric aromatic groups and a clean singlet for the
methyl protons (1.57 ppm). 19
F NMR shows only two
resonances corresponding to the PFCP ring substituted in a
symmetrical fashion.
PFCP aryl ether homopolymer P3 was prepared from
biphenol under similar conditions (Scheme 1). P3 shows a
Scheme 3. Model Reaction between OFCP and Sodium
Phenoxide
Figure 1. 19
F NMR spectrum of the model reaction product mixture.
Table 1. PFCP Polymers Molecular Weight, Polydispersity
Index (PDI), Thermal Properties, and Yield of
Polymerization
PFCP Mn Mw PDIa
Tg (°C)b
Td5%
(°C)c
yield
(wt %)
homopolymer P1 9100 22900 2.5 124 483 70
homopolymer P2 9600 11100 1.1 89 432 54
homopolymer P3 15450 29800 1.9 105 460 90
P3-co-P1d
5900 9300 1.5 94 325 74
copolymer (M1-alt-BP) 8400 14500 1.7 98 310 69
copolymer (M2-alt-6F) 2000 3000 1.5 68 224 51
a
GPC in THF using polystyrene as standard after precipitation in
methanol. b
DSC (heating rate 10 °C/min) in a nitrogen atmosphere.
c
TGA (heating rate 10 °C/min) in a nitrogen atmosphere. d
0.49/0.51
molar ratio of monomer 1/2 in copolymer as determined by 19
F NMR
spectroscopy.
Figure 2. (a) 1
H NMR and (b) 19
F NMR of PFCP aryl ether
homopolymer P1.
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3. higher number-average molecular weight of 15 450, with a PDI
of 1.9 (Table 1), relative to the above-mentioned homopoly-
mers (P1 and P2), with clean and well-integrated signals in
1
H NMR and 19
F NMR spectroscopy (Figure 4).
1
H and 19
F NMR spectra show no evidence of chiral carbon
atoms within the cyclopentene ring as would be expected in the
case of an addition rather than an addition−elimination
reaction. PFCP homopolymers (P1, P2, and P3) show
absorption in the ultraviolet spectrum (λmax 210 nm for P1,
P2 and 260 nm for P3) with no corresponding fluorescence.
Thermal analysis of these polymers shows unexpected
properties (Table 1). P1 exhibits a glass transition temperature
(Tg) of 124 °C, as determined by DSC, and a polymorphic
crystallization and melting at ca. 218 and 250 °C, respectively
(Figure 5a). The decomposition temperature (Td) at 5% weight
loss determined by thermogravimetric analysis (TGA) under
N2 was 483 °C for P1 with a number-average molecular weight
of 9100 (Figure 6). Remarkably, homopolymer P1 exhibited an
exceptional char yield of greater than 85% up to 800 °C.
DSC thermograms for P2 exhibited a glass transition temper-
ature of 89 °C. However, unlike P1, PFCP polymer P2 does not
show crystallinity under these conditions (Figure 5b), presumably
due to the decreased fluorine content as analogously observed for
the 6F-PFCB polymer.29
TGA analysis under a N2 atmosphere
shows that the decomposition temperature (Td) at 5% weight
loss exceeds 430 °C (Figure 6).
Figure 3. (a) 1
H NMR and (b) 19
F NMR of PFCP aryl ether
homopolymer P2.
Figure 4. 1
H NMR and 19
F NMR of PFCP aryl ether homopoly-
mer P3.
Figure 5. DSC thermograms of PFCP aryl ether homopolymer (a) P1,
(b) P2, and (c) P3.
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4. PFCP aryl ether homopolymer P3 exhibited an endothermic
transition determined by DSC of 105 °C (Figure 5c). Like P2
and unlike P1, P3 does not show crystallinity or melting
behavior under these conditions (Figure 5c). This higher
molecular weight homopolymer P3 gave decomposition
temperature of 460 °C (Td at 5% weight loss, Figure 6).
A random PFCP copolymer was also prepared in one step
with bisphenols and OFCP (Table 1). Reactions of variable
bisphenols with a slight excess of OFCP led to novel bis-
(heptafluorocyclopentenyl) aryl ether monomers (M1, M2)
and their step growth polymerization with other bisphenols
afforded PFCP copolymers with alternating arylene ether
structures (Scheme 4).
As seen earlier, biphenol gave higher molecular weight than
Bisphenol AF during polymerization with OFCP (P3 vs P1).
This may be due to the electron-withdrawing effect of the CF3
groups decreasing its nucleophilicity compared to biphenol.
Likewise, alternating copolymers of 6F containing monomer
M1 gave the highest molecular weight for identical copolymer
structures of different monomers (Table 1). This method
demonstrates a modular approach to alternating copolymers
from monomers of variable reactivity. Further, because of its
higher molecular weight, copolymer M1-alt-BP exhibits more
robust thermal properties than copolymer M2-alt-6F.
■ CONCLUSION
We have developed a step growth polymerization of bisphenols
with OFCP toward synthesis of a new class of perfluorocyclo-
pentenyl (PFCP) aryl ether polymers from commercial
feedstocks. PFCP polymers can be easily modified and func-
tionalized by using bisphenols with different spacer functional
groups. PFCP polymers exhibited very interesting thermal
properties with variable Tg depending upon the chosen
bisphenol. These polymers were obtained in good yields and
show high thermal stabilities under N2 with Td at 5% weight
loss ranging from 432 to 483 °C for homopolymers and 224 to
325 °C for copolymers. This new family of semifluorinated aryl
ether polymers can easily have phenolic or perfluorocyclopen-
tenyl terminal groups depending on the stoicheometry of the
reactants. Further, PFCP polymers contain main chain vinyl
ether groups for postpolymerization modification and potential
cross-linking.
■ EXPERIMENTAL SECTION
Chemical Reagents. Octafluorocyclopentene (99%) was pur-
chased from Synquest Laboratories and used as received. Bis-
(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF) and 4,4′-
biphenol were donated by Tetramer Technologies, L.L.C., Pendelton,
SC. Deuterated solvents were purchased from Mallinckrodt Chemicals
Inc. All other chemicals and solvents (analytical grade) were purchased
from Sigma-Aldrich and used as received unless otherwise stated.
Instrumentation. M1 and M2 and copolymers were characterized
on a JEOL ECX-300 MHz NMR spectrometer via 1
H, 19
F, and
proton-fluorine decoupled 13
C spectroscopy. P1, P2, and P3 were
characterized on a Bruker 400 MHz NMR spectrometer via 1
H, proton
decoupled 19
F, and proton decoupled 13
C spectroscopy. Chemical
shifts were measured in ppm (δ) with reference to internal
tetramethylsilane (0 ppm), deuterated chloroform (77 ppm)/
deuterated tetrahydrofuran (25.3 ppm)/deuterated acetone (29.8
ppm), and trichlorofluoromethane (0 ppm) for 1
H, 13
C, and 19
F NMR,
respectively. For coupled spectra, values are reported from the center
of the pattern. Attenuated total reflectance Fourier transform infrared
(ATR-FTIR) analyses of neat samples were performed on a Thermo-
Nicolet Magna 550 FTIR spectrophotometer with a high endurance
diamond ATR attachment. Ultraviolet−visible absorption and fluore-
scence spectroscopy were measured in THF on an Agilent 8453 UV−
vis spectroscopy system and Perkin-Elmer LS 50 B luminescence
spectrometer, respectively. Differential scanning calorimetry (DSC)
analysis was performed on a Mettler Toledo DSC 1 system in nitrogen
at a heating rate of 10 °C/min. The glass transition temperature (Tg)
was obtained from a second heating cycle using Star E version 10.0
software suite. Thermal gravimetric analysis (TGA) was performed on
a Mettler-Toledo TGA/DSC 1 LF instrument in nitrogen at a heating
rate of 10 °C/min up to 800 °C. Molecular weights for polymers P1,
P2 and P3 were measured by size exclusion chromatography (SEC)
analysis on a Viscotek VE 3580 system equipped with a ViscoGEL
column (GMHHR-M), connected to a refractive index (RI) detector.
GPC solvent/sample module (GPCmax) was used with HPLC grade
THF as the eluent and calibration was based on polystyrene standards.
For copolymers, gel permeation chromatography (GPC) data were
collected in THF from a Waters 2690 Alliance System with photo-
diode array detection. GPC samples were eluted in series through
Polymer Laboratories PLGel 5 mm Mixed-D and Mixed-E columns at
35 °C. Molecular weights were obtained using polystyrene as a
standard (Polymer Laboratories Easical PS-2).
Synthesis of PFCP Aryl Ether Homopolymer P1. In a 25 mL
Schlenk tube equipped with a magnetic stirrer was added 1.00 g
(2.97 mmol) of Bisphenol AF, 0.662 g (6.54 mmol) of triethylamine,
and 10 mL of DMF. The solution was degassed with nitrogen for
10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentene was added
via syringe; the Schlenk flask was heated slowly to 80 °C for 24 h. The
polymer was then precipitated in 100 mL of methanol, filtered, washed
several times with methanol, and dried under vacuum at 50 °C for
24 h, giving 1.1 g of a white powder (yield = 74%). 1
H NMR
(400 MHz, THF-d8, δ): 6.91 (dm, 3
JH‑2(H‑1) = 8.80 Hz, 4H), 7.32 (dm,
3
JH‑1(H‑2) = 8.80 Hz, 4H). 19
F NMR (376 MHz, THF-d8, δ): −63.85
(6F), −115.13 (4F), −130.17 (2F). 13
C NMR (100 MHz, THF-d8, δ):
Figure 6. TGA thermograms of PFCP aryl ether homopolymers P1,
P2, and P3.
Scheme 4. Bis(heptafluorocyclopentenyl) Aryl Ether
Monomers Synthesis and Polymerization
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5. 64.6, 110.8 (PFCP, CF2), 113.8 (PFCP, CF2), 117.5, 125.2, 130.8,
132.7, 134.9 (PFCP, CC), 155.2. FTIR (ν, cm−1
): 3150 and 3063
(H−CC), 1274 (C−O), 1151 (C−F), 780 and 658 (C−F).
Synthesis of PFCP Aryl Ether Homopolymer P2. Homopol-
ymer P2 was synthesized using the same method as P1, except it was
precipitated in a 0.5/0.5 volume ratio of water/methanol and washed
several times with a solution of 0.5/0.5 volume ratio of water/
methanol, giving a white powder after drying (yield = 90%). 1
H NMR
(400 MHz, acetone-d6, δ): 1.51 (dm, 6H), 6.69 (dm, 3
JH‑2(H‑1) = 8.91
Hz, 4H), 7.08 (dm, 3
JH‑1(H‑2) = 8.91 Hz, 4H). 19
F NMR (376 MHz,
acetone-d6, δ): −114.20 (4F), −129.71 (2F). 13
C NMR (100 MHz,
THF-d8, δ): 31.0, 42.7, 110.6 (PFCP, CF2), 114.1 (PFCP, CF2), 117.1,
128.5, 134.8 (PFCP, CC), 147.8, 153.0. FTIR (ν, cm−1
): 3130 and
3065 (H−CC), 1272 (C−O), 1142 (C−F), 782 and 654 (C−F).
Synthesis of PFCP Aryl Ether Homopolymer P3. Homopol-
ymer P3 was synthesized using the same method as P2, except the
reaction time was 36 h, giving a white powder after drying (yield =
50%). 1
H NMR (400 MHz, acetone-d6, δ): 6.92 (dm, 3
JH‑2(H‑1) = 8.58
Hz, 4H), 7.31(dm, 3
JH‑1(H‑2) = 8.58 Hz, 4H). 19
F NMR (376 MHz,
acetone-d6, δ): −113.89 (4F), −129.60 (2F). 13
C NMR (100 MHz,
acetone-d6, δ): 110.5 (PFCP, CF2), 114.0 (PFCP, CF2), 118.5, 128.8,
135.0 (PFCP, CC), 137.7, 154.5. FTIR (ν, cm−1
): 3151 and 3070
(H−CC), 2941 (C−H), 1270 (C−O), 1150 (C−F), 780 and 653
(C−F).
Synthesis of P3-co-P1. In a 25 mL Schlenk tube equipped with a
magnetic stirrer was added 0.793 g (2.36 mmol) of Bisphenol AF,
0.439 g (2.36 mmol) of biphenol, 1.052 g (10.39 mmol) of
triethylamine, and 10 mL of DMF. The solution was degassed with
argon for 10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentene
was added via syringe; the Schlenk flask was heated at 80 °C for 10 h.
The dissolved polymer was then precipitated in 100 mL of 0.5/0.5
volume ratio of water/methanol and washed several times with a
solution of 0.5/0.5 volume ratio of water/methanol and dried under
vacuum at 50 °C for 24 h, giving 1.7 g of a white powder (yield =
74%). 1
H NMR (300 MHz, acetone-d6, δ): 7.15 (m). 19
F NMR (282
MHz, acetone-d6, δ): −64.44 (m, 3F), −115.21 (m, 4F), −130.61 (m,
2F). FTIR (ν, cm−1
): 3150 and 3075 (H−CC), 1273 (C−O), 1150
(C−F), 787 and 661 (C−F).
Synthesis of M1. To a 50 mL round-bottom flask equipped with
a magnetic stirrer were introduced 2.00 g (5.95 mmol) of Bisphenol
AF, 2.77 g (13.1 mmol) of triethylamine, and 20 mL of DMF, and the
solution was degassed with argon for 10 min. 2.775 g (13.09 mmol) of
octafluorocyclopentene was then introduced with a syringe, and the
solution was heated slowly to 80 °C for 10 h. The solvent was then
removed, and the crude product was isolated by column
chromatography in dichloromethane (Rf = 0.93) to give 3.1 g of a
colorless oil (yield = 65%). 1
H NMR (300 MHz, CDCl3, δ): 7.19
(d, 3
JH‑1(H‑2) = 8.58 Hz, 4H), 7.43 (d, 3
JH‑1(H‑2) = 8.58 Hz, 4H).
19
F NMR (282 MHz, CDCl3, δ): −63.91 (s, 6F), −115.32 (d, 3
JF1(F‑2) =
9.84 Hz, 4F), −115.65 (d, 3
JF‑1(F‑2) = 13.11 Hz, 4F), −129.39 (s, 4F),
−146.61 (s, 2F). 13
C NMR (75 MHz, CDCl3, δ): 67.4, 105.5, 109.1,
111.1, 112.0, 118.3, 123.9, 131.3, 131.7, 138.0, 154.1. FTIR (ν, cm−1
):
3150 and 3075 (H−CC), 1270 (C−O), 1160 (C−F), 783 and 665
(C−F). GC-MS (m/z) [M + H]+
: 720.4 Elemental analysis: Calcd
(Found) C = 41.69 (41.62), H = 1.12 (1.03), F = 52.75 (53.03).
Synthesis of M2. M2 was synthesized and isolated with the same
method as described for M1 (Rf = 0.86 in dichloromethane) to give a
white solid (yield = 69%). 1
H NMR (300 MHz, CDCl3, δ): 7.25 (dm,
3
JH‑1(H‑2) = 8.61 Hz, 4H), 7.59 (d, 3
JH‑1(H‑2) = 8.61 Hz, 4H). 19
F NMR
(282 MHz, CDCl3, δ): −115.32 (m, 4F), −115.36 (m, 4F), −129.36
(s, 4F), −148.85 (s, 2F). 13
C NMR (75 MHz, CDCl3, δ): 104.3, 111.4,
114.1, 118.1, 122.2, 130.2, 131.2, 131.9, 153.9. FTIR (ν, cm−1
): 3133
and 3074 (H−CC), 1272 (C−O), 1145 (C−F), 787 (C−F). GC-
MS (m/z) [M + H]+
: 570.3 Elemental analysis: Calcd (Found) C =
46.33 (46.36), H = 1.41 (1.36), F = 46.64 (46.70).
Synthesis of Copolymer (M1-alt-BP). To a 25 mL Schlenk tube
equipped with a magnetic stirrer was added 0.500 g (0.694 mmol) of
M1, 0.129 g (0.694 mmol) of biphenol, 0.155 g (1.53 mmol) of
triethylamine, and 5 mL of DMF. The solution was degassed with
argon for 10 min, and the Schlenk tube was heated slowly to 80 °C for
10 h under stirring. The dissolved polymer was then precipitated in
100 mL of 0.5/0.5 volume ratio of water/methanol and washed several
times with a solution of 0.5/0.5 volume ratio of water/methanol,
giving a white powder after drying (yield = 51%). 1
H NMR (300 MHz,
acetone-d6, δ): 6.88 (m, 8H), 7.15 (m, 4H), 7.35 (m, 4H). 19
F NMR
(282 MHz, acetone-d6, δ): −64.45 (m, 3F), −115.02 (m, 4F), −130.6
(m, 2F). FTIR (ν, cm−1
): 315 and 3090 (H−CC), 2941 (C−H),
1265 (C−O), 1150 (C−F), 790 and 658 (C−F).
Synthesis of Copolymer (M2-alt-6F). The copolymer was
prepared using the same method as copolymer M1-alt-BP, giving a
white powder after drying (yield = 69%). 1
H NMR (300 MHz,
acetone-d6, δ): 6.72 to 7.19 (m, 8H), 7.26 to 7.45 (m, 8H). 19
F NMR
(282 MHz, acetone-d6, δ): −64.18 (m, 3F), −115.37 (m, 4F), −130.54
(m, 2F). FTIR (ν, cm−1
): 3130 and 3103 (H−CC), 2960 (C−H),
1263 (C−O), 1145 (C−F), 785 (C−F).
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: dwsmith@utdallas.edu.
■ ACKNOWLEDGMENTS
The authors thank Defense Advanced Research Projects
Agency (DARPA) for funding and Tetramer Technology
LLC for the gift of bisphenols. We also thank the Robert A.
Welch Foundation (Grant AT-0041), Intel Corporation, and
The University of Texas at Dallas for partial support.
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