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Lupine Publishers| Optimization of Chitosan+Activated Carbon Nanocomposite. DFT Study

Lupine Publishers | An archive of organic and inorganic chemical sciences

Abstract

First, the minimum energy (geometry optimization DFT-DMol3) is obtained among C48 optimized ring carbon-system, and one non-optimized chitosan copolymer unit. Second, C24 and C9 optimized rings, each one interacting with an optimized chitosan copolymer unit (Ch). With the aim to investigate structural properties, the first case is optimized by applying smearing; and the second without smearing. Two parallel hypothetical carbon chains of 12 carbon atoms, symmetrically arranged are optimized in C24 carbyne ring; and one hypothetical 5 carbon-chain parallel to another 4 carbon-chain end optimized in a cumulene C9-ring. These carbon-ring structures here defined as activated carbons (AC), correspond to big pore size diameter obtained without chemical agent acting on them. Single point calculations are to build potential energy surfaces with GGA-PW91 functional to deal with exchange correlation energies for unrestricted spin, all-electron with dnd basis set. Only in the first case, orbital occupation is optimized with diverse smearing values. To determine structure stability, the minimum energy criterion is applied on AC+Ch nanocomposite. To generate fractional occupation, virtual orbitals are formed in this occupation space, whether homo-lumo gap is small and there is certain density near Fermi level. This fractional occupation pattern depends on the temperature. It must be noticed that when AC and Ch are solids, there is no adsorption; however, by applying smearing it was possible to find potential energy surfaces with a high equilibrium energy indicating glass phase transition in Chitosan due to the chemisorption given at the minimum of energy. AC+Ch molecular complex nanocomposite is expected to be applied not only in medicine but also in high technology.

Introduction

With the aim to figure out a molecular complex formed through the interaction between a system of 48 carbons arranged in planar way and a copolymer unit of chitosan, potential energy surfaces were built [1,2] using single point step by step calculations. The problem is studied considering that a molecular complex is obtained by changing smearing value according to the energy value convergence. Considering that electrons occupy orbitals with the lowest energies and with an integral occupation number in calculations of density functionals, a smearing change indicates a fractional occupation in virtual orbitals within this space of occupation. The smearing calculations correspond to the explicit inclusion of the fractional occupation numbers of the DFT calculations, requiring an additional term to achieve a functional energy from variation theory [35]. The contribution of this term to the density functional force exactly cancels the correction term as a function of the change in the occupation number. For occupation numbers satisfying a Fermi distribution, the variation total-energy functional is identical in form to the grand potential [3-6]. From the grand canonical distribution or Gibbs distribution, the normalized probability distribution of finding the system in a state with n particles and energy 𝐸𝑛𝑟 [7], the Z grand partition function of the system, and the number of particles remains according to the Fermi energy ℰf =μ(T,V,n). When T = 0 the fermion gas is in the state of minimum energy in which the particles occupy the n states of 𝜓𝑖 of lower energy, since the exclusion principle of Pauli does not allow more than one particle in each state. Therefore, the Fermi function 𝑓(ℰ) gives the probability that certain states of available electron energy are occupied at a given temperature.

Other options for the shape of the occupancy numbers result from the different associated functional with finite temperature to DFT but without physical meaning, such as the temperature or the entropy associated with this term [3]. These terms, although numerically small must be included in the practical calculations that allow numbers of fractional occupation [3,8]. To consider the scope of smearing, it is known that electrons occupy orbitals with the lowest energies, and occupancy numbers are integers; nonetheless, there is a need for a fractional occupation in virtual orbitals within this space of occupation. We apply this when the HOMO-LUMO gap is small and there is especially a significant density near of Fermi level [9], thus in order to obtain the fractional occupation a kT term is implemented. This fractional occupation pattern depends on the temperature. The systems C48 carbinoid, C24 carbyne-ring, and C9 cumulene-ring (almost-planar) are arrangements obtained through DFT geometry optimization of two hypothetical parallel zigzag linear carbon chains. We consider these systems as carbon physically activated, due to the pore size diameter, and since no activating chemical agent has been applied. Carbyne is known as linear carbons alternating single and triple bonds (-C≡C-) n or with double bonds (=C=C=)n (cumulene) [10]. Polyyne is known as a allotrope carbon having H(-C≡C-) nH chemical structure repeating chain, with alternating single and triple bonds [11] and hydrogen at every extremity, corresponding to hydrogenated linear carbon chain as any member of the polyyne family HC2nH [12] with sp hybridization atoms. It is known that polyyne, carbyne and carbinoid have been actually synthesized as documented by Cataldo [13]. Bond length alternation (BLA) of carbyne pattern is retained in the rings having an even number of atoms [10]. Additional care must be taken with carbyne rings since the Jahn-Teller distortion (the counterpart of Peierls instability in non-linear molecules) is different in the C4N and C4N+2 families of rings [14-16]. There is a great variety of applications of activated carbon as an adsorbent material, and it has been used in areas related to the energy, and the environment, generating materials with a high-energy storage capacity [17].

Chitin is, after cellulose, the most abundant biopolymer in nature. When the degree of deacetylation of chitin reaches about 50% (depending on the origin of the polymer), it becomes soluble in aqueous acidic media and is called chitosan [18]. Chitosan is applied to remediation of heavy metals in drinking water and other contaminants by adsorption. The affinity of chitosan with heavy metals makes the bisorption process stable and advantageous, being only by the alginates present in brown algae matched [19]. The glass transition temperature of chitosan is 203°C (476.15 K) according to Sakurai et al. [20], 225°C (498.15 K) according to Kadokawa [21], and 280°C (553.15 K) according to Cardona-Trujillo [22]. One can differentiate specific reactions involving the -NH2 group at nonspecific reactions of -OH groups. This is important to difference between chitosan and cellulose, where three -OH groups of nearly equal reactivity are available [23,24]. In industrial applications, several solids having pores close to molecular dimensions (micropores < 20 Å) are used as selective adsorbents because of the physicochemical specificity they display towards certain molecules in contrast to the mesoporous substrates (20-500 Å) and macropores (> 500 Å). Adsorbents with these selective properties include activated carbon among others [25]. Chitosan-based highly activated carbons have also application for hydrogen storage [26]. In principle, electronic structure of diatomic molecules has been built through the overlapping knowledge of the interacting atomic orbitals [27]. In this case, the orbitals correspond to bonding (σg, πg) and antibonding (σu, πu) orbitals of hydrogen, carbon, nitrogen and oxygen diatomic molecules, whose H2, C2, N2, and O2 groundstate electronic configurations are and with 2, 8, 10 and 12 valence electrons, respectively. Actually, the reactivity sites in a molecule correspond to the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO). HOMO as base (donor), and LUMO as acid (acceptor) are particularly important MOs to predict reactivity in many types of reaction [28,29]. Activated carbon and chitosan have been independently applied as sorption materials to increase environmental quality standards. Then, we expect AC-Ch nanocomposite to have a powerful handleable adsorption property of pollutants that can be applied not only in wastewater treatment, but also in medicine against intoxication, in batteries to increase storage capacity, in electrodes of fuel cells, and in more possible applications, according to the pore size distribution to be generated on this new material.

Methodology

The interaction between an activated carbon molecule (AC) and a unit of the chitosan copolymer (Ch) is studied by means of DFTDMol3 [30-32]. The AC system is a hypothetical model of two parallel linear chains of 24 carbons each one geometrically optimized using DFT, converging into a plane molecular carbon system. In this system six nodes were formed allowing 7 interconnected rings of different bond lengths and sizes: 2 of 6 carbons, 4 of 8 carbons and one of 16 carbons. By summing these quantities gives 54 carbons since the carbons are in the nodes double counted. When subtracted they are the 48 carbons of the AC system. This system has a length of 28.4Å comparable to that of the chitosan copolymer unit (Ch). The reactants are AC + Ch corresponding to C48 + C14H24N2O9.

Single point potential energy curves were constructed [1,2] by using smearing. The following conditions to find AC+Ch (Activated Carbon+Chitosan) interaction energy are: functional GGA-PW91 [31,33-36], unrestricted spin, dnd bases, and orbital occupation with various smearing values. Considering that we obtained a solution for the energy value convergence, the interaction by changing the smearing value was studied. Since electrons occupy orbitals with lower energies and integral occupation numbers in calculations of density functional, a smearing change indicates fractional occupation and virtual orbital within this occupation space [19]. When generating a fractional occupation, virtual orbitals are in this occupation space generated, if the HOMO-LUMO gap is small, and there is certain density near the Fermi level [1], then it is implemented the fractional occupation term kT. This pattern of fractional occupation depends on temperature. Covalent connectivity calculations [37] according to DMol3 on no-bonding to s- and f-shell scheme, bond type, and converting representation to Kekulé, for bond length tolerances from 0.6 to 1.15 Ǻ were accomplished in this molecular complex mostly composed of carbon. Area calculations have been carried out by inserting triangles in each amorphous carbon ring and using the

Heron formula: where P=(a+b+c)/2 is the perimeter of a triangle of a, b, c sides; while the pore size diameter (PSD) is calculated as an approximation to the circle area. Periodic systems can be constructed using amorphous builder of BIOVIA Materials Studio, these are useful to calculate Radial Distribution Functions and the area under the curve on a significant interval.

Results

Chitosan Optimized by Applying Smearing

The default smearing value of 0.005Ha corresponds to T=1578.87 K and P=224.806 atm. We now exhibit electron smearing behavior using the known Fermi-Dirac statistic [38]. Facing two hydrogen atoms and using geometry optimization calculations, we built energy as a function of smearing value. Figure 1 shows the total energy variation when the system is optimized with respect to smearing value [39] (Figure 1). The fractional occupational pattern depends on the temperature, and this is derived from the energy change of Fermi distribution [6] as: 𝛿𝐸 = 𝑇𝑘; where k is Boltzmann constant. Considering a model in which the electrons are free and given that clouds of electrons are being a Fermi gas considered. The pressure is: 2/3 δE/δV [38]. From the latter two previous equations, temperature and pressure change is observed in Table 1 given the 𝛿𝐸 smearing energy. The planar molecular hypothetical system of 48 carbons is built by applying geometry optimization at two linear chains of 24 carbons as shown in Figure 2a, and the chitosan copolymer molecular system is built without applying geometry optimization, as observed in Figure 2b. Approaching enough these two molecular systems we studied a new molecular complex at different smearing values. The molecular model of carbon is symmetrically arranged in planar geometry, and it is physically activated through geometry optimization. We called activated carbon (AC) to the resulting planar carbon system. The length of this planar system is comparable to that one of chitosan (Ch). Each six-carbon ring has an area 4.34 Å2, each eight-carbon ring along with this has an area 8.74 Å2, each eight-carbon ring along with the sixteen-carbon ring has an area 8.55 Å2, and the sixteencarbon ring has an area 27.32 Å2. Considering each one of this area as circle areas the pore size diameter distribution is from 2.35 Å to 5.9 Å, which correspond to micropore size distribution of this carbon system. When considering the whole area of this system for calculating the pore size diameter 9.48 Å [40,41]. Chitosan is very well known to be macropore size [42].

Searching for a new molecular complex, Figure 3 exhibits the potential energy curve of the interaction between AC and Ch having equilibrium at (1.6Å, -1089Kcal/mol). In this case chitosan was not geometrically optimized in order to build the potential energy curve observed in Figures 3b & 3c. It was really easy to build this curve using smearing energy 0.05 Ha for every single point calculated, and hard to build it at 0.03 Ha. We also tried lower values than this, and we obtained poor or none results (Figure 3). After applying geometry optimization at smearing 0.05 Ha, and subsequently at 0.03 Ha. The smearing at 0.02 Ha is shown in Figure 4a. Then, we built the potential energy curve as shown in Figure 4b in step by step single point calculations for AC + Ch face to face interaction, when 2.264 Å is the separation between their corresponding centers of mass. The latter has a potential well depth of 165 Kcal/ mol at a distance of 2.2 Å, meaning formation of a new molecular complex at an adsorption energy greater than 20 kcal/mol in the chemisorption range [43] (Figure 4). Covalent connectivity [37] to the resulting system in Figure 4a was applied under the conditions previously mentioned in methodology, and the molecular complex observed in Figure 5 is obtained. In this complex the reactants and products are C48 + C14H24N2O9 and C49H3O3 + CH2 + C4H6O2 + CH3NO + C2H2O + CH2O + C2H2 + CHNO + CH3, respectively. Carbon bonds are single, double, and triple, as an example the C12 ring has eight double bonds, one triple bond, and three single bonds, where all the carbon valence electrons are shared. Furthermore, C8 and C16 rings have double bonds in one side of the ring, and single and triple bonds in the other side; and C6 ring has four double bonds and two single bonds. This whole carbon system has been activated by chitosan, and double bonds, and single and triple bonds are the representative characteristics of carbine-type molecules (Figure 5).

It must be noticed that geometry optimization of this whole system provides a lowest unoccupied molecular orbital (LUMO - electron acceptor) receiving an electron pair from the highest occupied molecular orbital (HOMO - electron donor). The donor HOMO from the base and the acceptor LUMO from the acid, combine with a molecular orbital bonding, which in our case corresponds to the orbitals 242-HOMO for E=-0.18317 Ha and 243-LUMO for E=- 0.17786, for a Fermi energy of -3136.28 Ha with A as irreducible representation of symmetry C1. The total orbitals number is 274. The orbital occupation is 202 A (2) plus 78 electrons in 65 orbitals, for a total number of 482 active electrons and binding energy of -22.997 Ha, at 2 steps. However, in order to get HOMO and LUMO drawn in this model, we run an energy calculation. Then, this molecular complex as seen in Figures 6a & 6b has HOMO-484 with E=-0.16398 Ha, LUMO-485 E=-0.16196 Ha, and Fermi energy Ef = -3161.44 Ha, for the reactivity sites with 482 active electrons. The total number of valence orbitals is 1070. The orbital occupation is 206 A (1) alpha and 206 A (1) beta, and 35.00 alpha electrons in 62 orbitals plus 35 beta electrons in 62 orbitals. HOMO as base-donor, and LUMO as acid-acceptor are the MOs locating possible reactivity in this reaction. An acid-acceptor can receive an electron pair in its lowest unoccupied molecular orbital from the base-donor highest occupied molecular orbital. That is to say, the HOMO from the base and the LUMO from the acid combine with a bonding molecular orbital in the ground state see Figure 6c.

After applying covalent connectivity [37] to the resulting system in Figure 6, we again applied geometry optimization for smearing 0.02Ha, and we obtain different molecular orbitals in the results, as shown in Figure 7. This molecular complex as seen in Figure 7 has HOMO-482 with E=-0.17650 Ha, LUMO-483 E=0.16060 Ha, and Fermi energy Ef = -3162.004 Ha, for the reactivity sites with 482 active electrons. The orbital occupation is 204 A (1) alpha and 204 A (1) beta, and 37.00 alpha electrons in 62 orbitals plus 37 beta electrons in 62 orbitals. The molecular complex observed in Figure 7 has the same products previously mentioned. It must be noticed that the lowest unoccupied molecular orbitals (LUMO-acceptor) only draw orbitals in the CH3 product, the rest of the molecular orbitals correspond to the highest occupied molecular orbitals (HOMOdonor) complex. Then, this is a very stable molecular system only allowing reactivity through the methyl radical CH3 (Figure 7) The potential energy curve in Figure 3b is very near to physisorption; however, smearing energy in this case corresponds with a very high temperature, which actually occurrs little inside sun surface. In this work, we gradually get down smearing energy searching until reaching the glass transition temperature of chitosan. The smearing energy value 0.02 Ha corresponds with temperature 6315.49 K according to Table 1, and it is still too high; however, is this way we have been achieving geometry optimization to reach right smearing values according to experimental measurements. After successful convergence in geometry optimizations at 0.01, 0.007, 0.005, 0.003, and 0.002 smearing energies, the convergence at smearing energy 0.0017 Ha has been unsuccessful after more than 10000 SCF iterations for an oscillating energy with an energy tolerance of 0.00002 Ha. After these calculations, we continued rising the smearing energy until 0.00175, and after more than 5000 SCF, convergence is successfully accomplished. The temperature 552.6 K reached for smearing at 0.00175 agrees with glass transition temperature range [498.15K, 553.15K] of chitosan, according to experimental measurements [20-22].

Figure 8 illustrates the final stage of the molecular complex formed. We can observe that while C48 has been deformed mainly in its planarity, the chitosan ended broken in the two initial groups of each polymer, also apparently divided in several smaller molecules. This fact is very well known experimentally, because one bonding solution (epichlorhydrine, glutaraldehyde, or EGDE -ethylene glycol glycidyl ether-) is commonly used to keep chitosan copolymer cross-linked for enhancing the resistance of sorbent beads against acid, alkali, or chemicals [19]. The products observed by applying covalent connectivity (under the bonding scheme for no bonding to s- and f- shell, covalent connectivity and bond type, and converting representation to Kekulé) are the following: C51H7NO4 + C4H6O2 + C2H2O + C2H2 + CH3O + CHNO + CH3. As it can be seen part of each polymer remain bonded to the AC system (Figure 8). Then, at smearing 0.00175 Ha we mostly obtain highest occupied molecular orbitals for the molecular complex observed in Figure 9. This output exhibits the orbitals a) HOMO-482 with an eigenvalue of -0.17013 Ha, b) LUMO-483 with an eigenvalue of -0.16923 Ha, and c) HOMOLUMO. The Fermi energy is Ef = 3162.0047053 Ha, for the reactivity sites with 482 active electrons. The orbital occupation is 238 A (1) alpha and 239 A (1) beta, and 2.96 alpha electrons in 5 orbitals plus 2.04 beta electrons in 4 orbitals.

Chitosan Optimized Without Smearing

First of all, the C24 carbyne-type ring alternating single and triple bonds is obtained by applying connectivity [37] and bond type to a C24 carbon ring which is the output of the input shown in Figure 10a corresponding to the geometry optimization of two hypothetical C12-carbon chains (Figure 10b). Then, Figure 10c exhibits an alternating single and triple bonds C24-ring. Second, applying clean of BIOVIA Materials Studio on chitosan copolymer molecule designed in Figure 2b, we obtain the input of a chitosan copolymer molecule as in Figure10d, and the Output exhibiting geometry optimization of the previous molecule is shown in Figure 10e. As we can observe, in this case chitosan remained complete. We made this, after suspecting that the initial bonds lengths and angles were not right in our design of chitosan, because broken chitosan is not a satisfactory result. Then, mixing the optimized C24 and Ch systems as shown in Figure 10f in the Input of a C24-ring surrounding a chitosan copolymer molecule, and after applying geometry optimization we obtain the Output of the previous CA-Ch nanocomposite see Figure 10g. Finally, we applied bonding scheme criteria as in Figure 10h.The nanocomposite in Figure 10h is a good example of the possibility of modifying the pore size distribution of chitosan when it is embedded into activated carbon. Here we consider INPUT and OUTPUT for applying geometry optimization on activated carbon and chitosan C14H24N2O9 system after each part has been previously optimized, and we also applied bond criteria for connectivity, bond type and kekulé representation. The C24-ring is carbyne type, and the chitosan copolymer molecule has been optimized in three dimensions in this case. The position of C24- ring surrounding a chitosan copolymer molecule has been only proposed.

From the interaction through geometry optimization of two linear carbon chains of four and five carbon atoms as in Figure 11a, cumulene C9-ring shown in Figure 11b is obtained. This is a clear evidence of Jahn-Teller effect, because we observe double bond lengths alternating long/short with a difference among .02 and .03 Å, and the angles in this non-planar (Figure 11b) cumulene molecule are also different. The expected angles in a planar symmetrical molecule should be the same according to a well-defined symmetry. We considered the interaction of chitosan with another almost planar carbon ring of nine carbon atoms, now one in front to the other as in Figure 11c. Then, in Figure 11d there is another example about building pore size distribution among chitosan and activated carbon. In this case, we consider INPUT and OUTPUT for geometry optimization of cumulene C9-ring and chitosan C14H24N2O9, each one previously optimized by applying geometry optimization to the whole system, and also considering the bond criteria for connectivity, bond type and Kekulé representation as shown in Figure 11e. The cumulene C9-ring and chitosan copolymer molecule have been optimized in three dimensions, and we clearly observe the cumulene passing from face to face to almost T-shape orientation taking three hydrogen atoms from chitosan. The input position of cumulene C9 ring face to face with chitosan in that precise location has been proposed, and the result has been excellent.

Discussion

We consider each carbon ring as physically activated through geometry optimization, due to pore size diameter remains in the average size compared against experimental measurements [41]. The C48 optimized ring carbon-system and one non-optimized chitosan copolymer unit has been studied considering the result after geometry optimization, as a molecular complex obtained when smearing value changes for converging energy values. Different elongation among single and triple carbon bonds in the carbyne-type are due to Jahn-Teller effect [14]. Then, C24 carbynering when we optimize two carbon chains at 3.074 Å of separation distance, is due to the Jahn-Teller effect. The Jahn-Teller effect is also present in C48 carbinoid -ring for their C8- and C4- carbinoid -rings. Carbon rings C4N (N<~8) exhibit a substantial first-order Jahn-Teller distortion that leads to long/short (single/triple) bond alternation decreasing with increasing N [14]. Whether we want to draw HOMO-LUMO orbitals, it is necessary to ask for orbitals in the geometry optimization as input data. At this work, for smearing energy 0.02 Ha we found different HOMO LUMO orbital numbers among the initial system in Figure 5 without asking for orbitals in the geometry optimization calculation, and its output asking for orbitals in a new energy calculation shown in Figure 6. Again after practicing connectivity, bond type, and Kekulé representation at smearing energy 0.02 Ha, we asked for orbitals, and we found in Figure 7 a small change at the orbital numbers previously obtained, and the corresponding energies were little different to the previous ones. We infer that bonding type change produced the differences, and the correct values correspond to the correct bonding type in the new molecular complex system formed.

The strongly dependence on smearing means very closely spaced energy levels (high degeneracy) near Fermi level. When there is a degenerate electron state, any symmetrical position of the nuclei (except when they are collinear) is unstable. As a result of this instability, the nuclei move in such a way that the symmetry of their configuration is destroyed, the degeneracy of the term is being completely removed [44,45]. High degeneracy indicates a high symmetry of the molecule, then the system tends to be distorted, in such way that when moving, the occupied levels are down and the unoccupied ones are up [46]. When levels are very densely spaced, convergence is hard to reach, since very small changes will occupy completely different states, and we get oscillations. These can be damped by smearing out the occupancy over more states, so that we turn off the binary occupancy of the states. We get down smearing width to glass transition temperature by decreasing the smearing parameter in steps to gradually stabilize our molecular complex system at the right temperature.

We initially observe distortion of chitosan system, and then its possible breaking in some products. This is partially in agreement with the results presented by Chigo et al. [46] in a study of the interaction among graphene-chitosan for a relaxed system doped with boron, in which they consider the interaction of pristine graphene with the monomer of chitosan (G + MCh:C6H13O5N) in different configurations, whereas we consider a chitosan copolymer molecule: C14H24N2O9 in only one orientation. While Chigo et al. [46] found a perpendicular chitosan, molecule linked to a carbon nanotube system, we obtained a cumulene carbon ring almost perpendicularly linked to a chitosan copolymer molecule.

Conclusion

We found one mechanism to figure out an optimized big molecular complex system by using DFT geometry optimization. This mechanism is based on smearing calculations, and on decrements of smearing energy in the molecular complex system until reaching the glass transition temperature of one of the components, which in this case correspond to the chitosan copolymer molecule. In order to get a molecular complex system AC + Ch, it is needed a high temperature among them at least to the phase transition temperature of either AC or Ch, because when they are solids there is only a heterogeneous mixture at room temperature. The use of smearing allows to reach high temperatures because according to Table 1 temperature increases as the smearing energy increases. We observed that the use of smearing to optimize a molecule as complex as the chitosan causes this to be fractionated, nevertheless when putting it in a plate of coal we obtained the glass transition temperature of the chitosan reported experimentally. The potential well depth providing chemisorption indicates existence of phase transition in one of our two molecular systems. This phase change is attributed to chitosan, due to carbon is more stable, and because we reach glass transition temperature of chitosan when dealing with the whole molecular complex system. In addition, when applying covalent connectivity, the activated carbon is the most stable molecular system keeping its molecular structure. According to HOMO and LUMO in Figures 6 -9, the sites with the greatest reactivity correspond to double and triple bonds. Besides, Figure 9 exhibits one amine functional group linked to the carbon system now C51 carbon molecular complex formed with a particular pore size distribution. Considering that after geometry optimization physisorption provides bonding in two parts of the chitosan molecule, this is an indication of a more environmental linking than that caused by cross-linking solutions, because cross-linking solutions might be toxic in medicine applications. The first chitosan molecule used, and optimized using smearing resulted to be unstable, because finished broken in several products. The second chitosan molecule used, and optimized without smearing, or with a very small smearing value resulted to be very stable, on which we were able to add activated carbon and to obtain good results. We have been able to optimize chitosan and add activated carbon, and we have observed the change in pore size distribution, even though we are missing its calculation, to assign the type of material obtained (micropore, mesopore, or macropore). We are working on it.

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blogrevolve2020 · 4 years ago

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The SBB Research Group in Chicago's Center for Neighborhood Stabilization

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juniperpublisherscasestudies · 5 years ago

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Juniper Publishers- Open Access Journal of Case Studies

Juniper Publishers-Open Access Journal of Case Studies

Authored by Elena Kochova

Abstract

X-Linked adrenoleukodystrophy (ALD) is a rare neurodegenerative disorder with a wide clinical spectrum. It is characterized by progressive cerebral demyelination, spinal cord axonal degeneration and adrenal and testicular insufficiency. ALD is caused by mutations in the ABCD1 gene, involved in the metabolism of fatty acids. The main biochemical feature is elevated plasma and tissue levels of very long-chain fatty acids and the diagnosis relies on their measurement in plasma along with MRI studies. Allogeneic bone marrow transplantation is the preferred treatment in patients with the severe, cerebral form of ALD, offering a halt in disease progression, but only when instituted in the early stages of cerebral demyelization. The aim of this review is to summarize the present understanding of ALD, as well as to overview the advances in the diagnostics and treatment.

Keywords: Adrenoleukodystrophy, X-linked, Hematopoietic stem cell transplantation, ABCD1

Abbreviations: ABC: Adenosine Triphosphate - Binding Cassette; ALD: Adrenoleukodystrophy; ALDP: Adrenoleukodystrophy Protein; ALDRP: Adrenoleukodystrophy Related Protein; AMN: Adrenomyeloneuropathy; Cr: Creatine; Ch: Choline; HSCT: Hematopoietic Stem Cell Therapy; MR: Magnetic Resonance; MRI: Magnetic Resonance Imaging; NAA: N-Acetylaspartate; VLCFA: Very Long Chain Fatty Acids

Introduction

Adrenoleukodystrophy (ALD) is an X-linked inherited disorder that affects the central nervous system, peripheral nerves, adrenal cortex and testes. Also known as Schilder’s disease and sudanophillic leukodystrophy, ALD is a peroxisomal metabolic storage disease caused by mutations in the ABCD1 gene, involved in the degradation of very long-chain fatty acids (VLCFA). The consequent accumulation of VLCFA leads to progressive central demyelination and adrenal insufficiency.

The first case of X-linked ALD (X-ALD) was likely described in 1910 [1]. Siemerling and Creutzfeldt in 1923 described it as “bronzed sclerosing encephalomyelitis” [2]; another synonym for ALD is Siemerling-Creutzfeldt disease. Biaw [3] in 1970 assigned the term adrenoleukodystrophy [3]. Since then, significant advances have been made in elucidating the pathophysiological mechanisms of the disease, as well as in the diagnostic and therapeutic approaches.

X-ALD is a rare disease, with an overall estimated incidence of 1:17,000, including symptomatic female heterozygotecarriers [4]. This makes it the most common of the leukodystrophies. The clinical presentation of ALD is strikingly diverse, from rapidly progressive, fatal neurological involvement in young children, to slowly progressive adrenomyeloneuropathy in older children or adults. The symptoms of ALD overlap with the other numerous leukodystrophies which makes the diagnosis of ALD challenging.

Genetics and Pathophysiology

The breakthrough in the ALD field came in 1993 when mutations in the ABCD1 gene were identified in patients with ALD [5]. The gene is mapped to Xq28 and encodes the adrenoleukodystrophy protein (ALDP), one of four members of the peroxisomal subfamily of ATP-binding cassette (ABC) proteins. ALDP is involved in the transport of very long-chain fatty acids (VLCFA) from the cytoplasm into the peroxisomes, where the oxidation and degradation of VLCFA takes place.

A gene that is closely related to ABCD1 has been mapped to chromosome 12q11. This gene is referred to as ALDR or ABC2. Its gene product, referred to as ALDRP, has 66% homology to ALDP [6], is also localized to the peroxisomal membrane and can correct the defect in very long chain fatty acid metabolism in cultured fibroblasts of X-ALD patients. The relationship between ALDP and ALDRP is still unclear, but it has been proposed that variations in the expression of ALDRP may account for the wide range of phenotypic expression that is a specific feature of X-ALD. Also, these similarities between ALDP and ALDRP have led to the hypothesis that over expression of ALDRP might be used as a therapeutic strategy.

The inactivating mutations in the adrenoleukodystrophy gene, most of which are unique to particular families, have been defined in more than 400 families. In general, there is no correlation between the nature of the mutation and the phenotype. In one family the same mutation was associated with 5 widely different phenotypes [7]. De novo mutation of ABCD1 occurs in less than 8% of ALD patients [8].

The defect in the ALDP results in accumulation of VLCFA, which in turn produces an intense inflammatory response in the white matter of the central and peripheral nervous system. The VLCFA accumulation itself is thought to be responsible for the adrenal and testicular involvement. The inflammatory mechanism that leads to demyelination is not completely understood, but thought to result from activation of brain macrophages and astrocytes bearing CD1 molecules that recognize lipid antigens which are abnormally acylated by the excessive VLCFA. The precise mechanism by which the accumulation of VLCFA leads to the inflammatory demyelination that is the cause of the neurologic disability is still unclear.

Clinical Presentation

Most male X-ALD patients develop adrenocortical insufficiency in childhood and progressive myelopathy and peripheral neuropathy in adulthood. A subset of male patients, however, develops a fatal cerebral demyelinating disease, cerebral ALD. Female carriers can also develop progressive myelopathy and peripheral neuropathy, but generally at a later age than males. They only very rarely develop adrenocortical insufficiency or cerebral ALD. The three major disease categories are:

The severe, cerebral demyelinating form (cerebral childhood form) - appearing in mid-childhood (4-8 years);

Spinal cord demyelination and axonal degeneration (adrenomyelopathy, AMN) - occurring in men in their 20s or later and older women.

Impaired adrenal gland function (Addison’s disease or Addison-like phenotype). AMN is the most frequent form, affecting 60% of affected males and 50% of female carriers [4].

The cerebral childhood form occurs in approximately 35% of ALD patients. The mean age of onset is 7 years, with the earliest onset noted at around 3 years. It develops in three phases:

A.An asymptomatic latent phase, when there are no clinical signs, but MRI changes of demyelination are present (the first lesions can be evident at around 4 years of age);

C.A terminal phase with significant motor, sensory and cognitive sequellae, which leads to coma and death.

The symptoms depend on the topography of the demyelienation. The parieto-occipital forms are the most frequent [4], the initial symptoms consisting of cognitive visuomotor and visuospatial abnormalities and immediate memory deficits. Behavioral changes ensue, such as hyperactivity or attention deficit and emotional troubles, along with sensory disorders (visual field amputation, diminishing visual acuity, impaired auditory discrimination) and motor disorders (pyramidal syndrome of the lower extremities, gait abnormalities, hemiparesis, cerebellar ataxia). Sometimes seizures also occur. Once the symptoms appear, they progress rapidly and lead to an almost absolute loss of all cognitive functions, tetraplegy and blindness, and a vegetative state ensues usually within 3 years.

The frontal form presents with a frontal syndrome and hemiparesis. Sometimes adrenal insufficiency is the first sign of the disease, appearing well in advance of the neurological symptoms. The cerebral demyelinating form of ALD can also occur at a later age or in adulthood, when it assumes a progressive course similar to the childhood form.

Adrenomyeloneuropathy (AMN) is the more frequent form of ALD. The symptoms appear at an age of 20-30 in men and 40-50 in half of the female carriers and typically consist of spastic paraparesis with disturbed gait as a result of posterior spinal cord degeneration and urinary problems such as dysuria and urgency. Sometimes clinical signs of peripheral neuropathy (demyelinating, axonal, or both) can be seen. The symptoms are progressive and lead to a significant motor disability, but the progression varies and can extend over 20 years, without remission.

Adrenal insufficiency may be diagnosed after the appearance of neurological symptoms or decades in advance. Testicular dysfunction usually occurs late in the course of the disease. AMN in female carriers assumes a less severe form; the peripheral neuropathy is rarer, but neurogenic pain is a more frequent and severe feature. A certain percentage of men diagnosed with AMN will later develop the cerebral form. There is no biological marker that can be used for predicting the evolution of the disease on an individual level, but in general the earlier the onset, the faster the progression [4].

A significant proportion of the patients with ALD will develop adrenal insufficiency at some point [9], which affects primarily the glucocorticoid, followed by the mineralocorticoid function. ALD is the most frequent cause of adrenal insufficiency in males over the age of 4, and the second most frequent cause of adrenal insufficiency in adults [9]. It assumes the usual clinical presentation - melanodermy, followed by adrenal crisis with its usual clinical presentation. It can be the only sign of ALD for decades before the appearance of neurological signs.

Diagnostic Workup

The diagnosis of ALD is primarily based on biochemical and MRI studies. The biochemical signature of ALD is elevated plasma VLCFA levels, present in all affected males. Three parameters are analyzed: the concentration of C26:0, the ratio of C24:0 to C22:0 and the ratio of C26:0 to C22:0. All three parameters are usually elevated. With methodological advances, false positives and false negatives in males are exceptionally rare. The abnormality is present at birth and remains relatively constant throughout life. In contrast, only a proportion of female carriers have elevated plasma VLCFA; therefore targeted mutation analysis is the most effective means for carrier detection. MRI diagnostics are of great value, most frequently showing signs of symmetrical demyelination, with contrast accumulation at the edge of the lesions.

In the childhood cerebral form, MRI of the brain shows signs of demyelination with hyposignal in the T1 sequence and hypersignal in the T2 and FLAIR sequence, which allows for localization of the lesions and evaluation of the inflammatory character of the lesions based on the gadolinium uptake. Cortical atrophy can be seen in the later stages [4]. Studies have shown that the degree of MRI abnormality as assessed by the Loes scoring system [10], when coupled with age, aids in predicting the future course and in selecting patients who are candidates for bone marrow transplantation [11].

Newer modalities like MRI spectroscopy have provided new inputs into the disease.Proton MR spectroscopy is useful for determining the early signs of disease in patients even when MRI is still normal. MR spectroscopy shows abnormal metabolite ratios in the areas of abnormal T2 signal, but also in normal-appearing brain regions, including a decrease in N-acetylaspartate (NAA)/Creatine (Cr) and NAA/Choline (Ch) and an increase in Ch/Cr [12]. Lipids-lactate peaks are also valuable markers for the demonstration of the presence and progression of lesions. The metabolic ratio alterations seem to be proportionate to the severity of the ALD phenotype. Interestingly, higher VLCFA levels are associated with a lower NAA/Cr ratio [13].

The spectroscopic changes are not disease-specific, but are a sensitive indicator of disease progression [14] and can be useful in the evaluation of therapeutic interventions [15]. In AMN, cerebral and spinal MRI shows no changes in the early stages of the disease. The lesions, namely progressive atrophy of the spinal cord, appear in the later stages, but never show gadolinium uptake. Spectroscopy reveals axonopathy in the morphologically normal cerebral white matter, with reduced NAA/Cr and NAA/ Ch, most prominent in the internal capsule and parieto-occipital white matter [16].

Although MR abnormalities are rare in heterozygous women, even when symptomatic [17], the spectroscopy shows axonal abnormalities, which may be indicative of the distal axonopathy that represents the principal neuropathological change in AMN [18]. Wilken and colleagues examined the prognostic significance of MR spectroscopy for patients who received bone marrow transplants [15]. They found an association between outcome and the N-acetylaspartate levels in affected brain white matter. A high level was associated with a positive outcome, whereas low levels had a negative predictive value, as did increased levels of choline-containing compounds. Abnormal NAA/Ch ratios in the regions adjacent to the MRI lesions are a negative predictor for progression [14].

Genetic testing for ABCD1 mutations is useful in the identification of female carriers, as they may have normal VLCFA levels. This investigation should be performed in all females who are at risk of being a carrier for ALD, but is only possible when the mutation in the family is known. Prenatal diagnosis is important for the prevention of the disease, and is performed by measuring VLCFA levels in cultured amniocytes and ABCD1 mutational analysis in chorionic villus samples.

Therapeutic Options

The application of immunomodulatory and immunosuppressive drugs has failed to prevent progression of cerebral neuroinflammation. Initially proposed treatments were Lorenzo’s oil and statin therapy as well as VLCFA intake restriction, but clinically relevant benefit from such treatments has not been proven and they remain controversial. The preferred treatment option for preadolescent patients in the early stages of childhood cerebral ALD is allogeneic hematopoietic stem cell transplantation (HSCT).

This therapy was first described in 1990 [19] and several studies have shown promising results, when the treatment is performed early in the course of cerebral involvement and a human antigen-matched donor is available. The procedure can stop the progression of demyelination and stabilize the neurological symptoms. The outcome is significantly better when there are no neurological deficits and the MRI Loes severity score is less than 9 at the time of treatment. Despite the success of HSCT reports, numerous factors complicate the widespread usage of this treatment for ALD patients. The procedure should not be performed in patients with advanced disease, as the treatment is unable to stabilize neurological involvement in patients with advanced ALD.

It has been shown that MR spectroscopy might be predictive of clinical outcome after HSCT and may be further substantiated by using additional new imaging approaches, such as diffusion tensor imaging and magnetization transfer MRI [20]. While disease progression of patients before HSCT is mainly characterized by a further increase of elevated cholinecontaining compounds as an indicator of active demyelination, a positive outcome after HSCT is found to be correlated with high NAA levels in affected white matter before HSCT.

The positive effects of HSCT when instituted at an early stage of the disease may validate the efforts to institute newborn screening programs [21]. The benefit of HSCT was also shown for the first time in a patient with adult-onset ALD, with only mild symptoms remaining 2 years post-treatment [22]. The overall transplant-related mortality in HSCT patients is relatively high and non-myeloablative HSCT is being introduced as an alternative to myeloablative HSCT, with promising outcomes. For patients where a matched donor is unavalaible, umbilical cord blood stem cells are an alternative.

4-Phenylbutyrate (4-PB) has attracted interest as a potential therapeutic option for ALD. It has shown to improve the capacity of cultured ALD-cells to metabolize VLCFA. In the mouse model, it was shown that 4-PB reduces VLCFA levels in the brain and adrenal gland. 4-PB has the effect of increasing the expression of ALDRP, which, as noted previously, may be able to substitute for the function of ALDP. Its clinical effects have not yet been evaluated. ABCD2, the gene encoding ALDRP, when over expressed in cultured human fibroblast cell lines from ALD patients can normalize peroxisomal β-oxidation and prevent accumulation of VLCFA. Thus, the pharmacological induction of ABCD2 should be able to compensate for the lack of functional ABCD1 and is a potential attractive therapeutic target. Pujol and coworkers have shown that valproic acid induces expression of ABCD2 in human ALD fibroblasts. Other potential therapeutic strategies such as antioxidant therapy and neuroprotective therapy with insulin-like growth factor and neurotrophin-3 are being experimented upon. Preliminary work using lentiviralbased gene therapy in two young ALD patients shows short-term neurological benefits similar to HSCT [23].

It is now clear that early diagnosis is perhaps the single most important factor in treating ALD patients as there is no effective treatment for patients experiencing severe neurological symptoms. Efforts to add newborn screening for ALD and other peroxisomal disorders are moving forward; ALD screening has been initialized in the Netherlands as of 2015 and the USA since 2016. As in many fields, advances in gene therapy have the potential to revolutionize the treatment of ALD.

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iamjoffeth · 6 years ago

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instantgotheggbanana-blog · 6 years ago

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Repost ❤️ Hi guys share ko lng my story. Napansin po ng iba n lumalaki ang Leeg ko kya nmn nag decide ako magpacheck up, nun july 31 2018 pinacheck up ko ang Leeg ko s sacred heart malolos bulacan at ang doctor ko ay c Doctora Gutierez bngyan nya po ako ng ibat ibng klase ng request para s ECG, thyroid Ultra sound, Fa, TSt, FT3, Ft4, CBC at yun n nga po n diagnose ako may Goiter bngyan nya ako ng mga gmot n iinom hanggang july 25 2019 ko dw iinom ang sbi nya po 1 to 2 years ang gamutan,,sinunod ko po ang mga reseta nya kYa ininom ko dn ang mga gmot dhil takot ako lumalala.. pero makalipas ang ilang buwan lalo syang lumaki natakot po ako halos ndi nako mkpg labas ng leeg ko at makaharap s tao, ndi nrin ako nkpunta s ofc ng aim dhil s hiya ko s Leeg ko.. Pinakita ko po s upline ko kay up maribel Maribel Domondon Aguirre sbi nya part member k ng aim gumamit k ng product sbi ko s sarili ko Oo nga subokan ko nga ang c24/7 nagtry po ako yun kape nmin n Liven coffee ininom ko at Yun product nmin c24/7 sbi nila mag mega dos dw ako e ndi ko kaya kc ang mega dos 9cupsul a day ang ginawa ko yun liven coffee limang beses s isang araw ko kinapi tas ang c24/7 1 cupsul a day sinabay ko po ang fudsupplement s gmot n nireseta saakin ni Doctora gutierez and sobrang thank you Lord tlga napakabuti ng panginoon after 4months n uminom ako wla n po ako makita khit maliit ng bukol s Leeg ko ndi p po tpos ang gamotan ko s july 25 2019 p ako pinapabalik ng doctor ko pero yun Leeg ko po wla ng bukol,.. Sobrang blessed ko po tlga khit mdmi pagsubok tlga tayo dn po ang ggawa ng sulosyon s mga dumarating saatin pagsubok. Gusto qlng po ishare hwg tayo mawalan ng pag asa khit anong sakit ang dumapo saatin ggaling at ggaling tayo bsta my paraan tayo..Nsa Dios ang awa nsa tao ang gawa.. Salamat c24/7 n product ng aim global at higit s lahat salamat Lord napakabuti mong tunay at proud ako ishare ito upng mdmi png tao matulongan ang produkto https://www.instagram.com/p/BxEDjh_Fly8/?utm_source=ig_tumblr_share&igshid=1mx8ii05rpowc

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christianreybariso · 5 years ago

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Another product testimony using our food supplement of C24/7 and Complete Phyto-Energizer. Here's her share testimony. Kindly read and digest.. Sobrang Proud ako kase isa ako sa na tulungan ng C24/7 noong nagka dengue ako and ngayon naman yung nakababata kong kapatid na si Barbielyn Lat, Napansin ko kapatid ko na may bukol sa leeg nung una maliit lang siya habang tumatagal lumalaki, and since member ako Aim Global and malaki tiwala ko sa products sabe ko sa kapatid ko mag take ka COMPLETE, 2 capsule 30 minutes before meal, pinag take kona agad siya kahit hindi pa namen siya napapacheck up! Kase ayaw niya umabsent sa school at alam ko din naman safe ang products ng AIM dahil sa all natural na laman nito pwedeng pwede magtake may sakit ka man o wala. After 2weeks pina check up na namin siya akala ko nung una baka goiter ang sakit ng kapatid ko kase lumalaki ang Leeg niya. After check up sabe ng doctor nodules bukol sa Leeg need niya ipa - ultrasound para malaman kung cancerous ba ito o hindi tapos tinanong namen si Doc, kung bakit nagkaron ang kapatid ko ng nodules san nakukuha ung sakit na nodules? Sabi ni Doc, nasa lahi po siya wala din po sa kinakaen, syempre natakot kame kinabukasan ipina ultrasound agad namen ung leeg ng kapatid ko.. After pa ultrasound ayon Right thyroid is Normal and Left thyroid is Enlarged, means malaki na ung bukol sa leeg ng kapatid ko after pa ultrasound at nakuha namen ang result ng ultrasound balik kame kay Doc. Para ipa basa yung result ng ultrasound, sabe ni Doc, hindi naman siya cancerous at walang gamot sa sakit na to kelangan lang ipatusok naten ung bukol sa leeg ng kapatid mo para matangal ung tubig na nasa leeg niya na nagiging sanhi ng paglaki ng leeg niya. Hangang sa binigay ng doc.ang pangalan ni DR.Colly Gonzales (Surgeon) na magtutusok don sa leeg ng kapatid ko at kung san hospital Lipa Medix Medical Center. Inabot na kame ng hapon hangang sa hindi na namen pinuntahan ung sinasabe ni doc. hindi na namen pinatusok ang bukol sa leeg ng kapatid ko habang tuloy tuloy ko pa rin siya pinagtatake ng COMPLETE... Continue reading.. https://m.facebook.com/story.php?story_fbid=1430412453811897&id=124026601117162 https://www.instagram.com/p/CAsUSZqjS4e/?igshid=u4c848dwh05a

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yuandya1234 · 5 years ago

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amazingc247-blog · 6 years ago

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REPOST!!!! You can save a life through sharing this Cherie Ballenas Acejo Another testimony of how really effective our #AIMGLOBAL #PRODUCTS😊 July 12, 2018 when I was decided to join in AIM GLOBAL FAMILY. Last July 21, Day 1. my brother was in bad condition...dinala po siya sa James Gordon Hospital, Olongapo City.,dahil nakaramdam siya ng pamamanhid sa kanang parte ng katawan nya, hindi nya macontrol ang galaw ng kanyang paa at braso. Pina CT scan siya agad at yung findings, Cerebellar Infract daw.,or Mild Stroke. May naipit na ugat at naapektuhan ang pagcontrol ng movement ng mucles niya. Pero nakakausap pa namin siya, siya yung tumatawag sa akin dahil nasa antique pa ako. Na kwento ko sa dalawa kung upline sir Kurt Narzo at upline Mrs Nenita Good, ang nangyari sa kapatid ko. 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July 24 tuesday Day 4, dumating kami 6pm, its breaks my hearts nung makita ko kapatid ko, maraming nakakabit sa kanyang life support. Pero ng dumating kami nagigising.gising na din siya, dahil may gamot na iniinject sa kanya. Pero ang bilis nyang makatulog ulit. So Kina.usap ulit kami ng nuerosurgeon na oopera sa kanya, na kung hindi kaagad maoperahan, tuluyan na daw siyang matutulog..lifetime daw. pero sabi ko observed muna namin ng ilang araw saka na kami magdisisyon kung wala paring improvement. Dahil na lock yung jaw nya hindi nya maibuka yung bibig nya. Pa sikreto lang, Bumili kami ng dropper yun ang ginamit ko para makainom siya Vida Juice...maya maya ko siya pinapainom.7pm ko siya sinimulang painumin after 2 hrs nagkakamalay na sya dumidilat.dilat ang mata niya pagginigising namin, unti.unti nya kaming nakikilala. Yung choleduz at c24/7 hinalo ko sa vida juice nya at nilalagay ko sa NGT nya pagkalabas ng nurse na naglalagay din ng food nya. 24hours ko siyang binantayan at pinapainom ng Vida juice. Maya.maya ko siya kinakausap. July 25, Wednesday Day5 Pag round ng 2 Doktor, laking gulat nila, pagtest nila sa kapatid ko: dilat mata, taas kamay, taas paa, labas dila,...100% nagawa nya lahat. Limang beses siyang binalik.balikan ng nurse at doktor ng buong araw at paulit.ulit siyang tinest. Sabi ng nurse MILAGRO daw. Tinuloy tuloy ko lang ang pag bigay sa kanya ng Supplement..araw.araw may improvement siya.. Day 6: tanggal Oxygen Day7:tanggal NGT Day8:tanggal Catheter Day10:Punta CR alalay lang, naligo. Day12:tanggal Dextrose Day14:GoodbyeHospital Tama naniniwala akong MILAGRO talaga, Lahat ng Nangyari, plano ni LORD. 9 days palang akong member ng AIM GLOBAL bago na STROKE kapatid ko. Hindi pa na STROKE kapatid ko binigay na ni LORD ang solusyon sa problema namin. AIM GLOBAL PRODUCT at AIM GLOBAL FAMILY ang ginawang instrumento ni LORD upang mabigyan ng Second Life Kapatid ko. nagpapasalamat po ako ng TAOS PUSO sa mga taong kinasangkapan ni LORD, dahil po sa inyong malasakit at pag gabay sa akin..nabigyan ng Second Life ang kapatid ko..Upline Doc Jing Baladad at Doc Bing Frangue Baladad sir Kurt Narzo, Mam Mrs. Nenita Good. At sa lahat.lahat po ng pamilya, kaibigan, katrabaho at AimFamily namin na nag.alay ng prayers para sa kapatid ko maraming.maraming salamat po. Thank you din po sa Family ni Mam Sheanne Medina, may.ari po ng BCO olongapo. Ito po ang testimony ko sa mga product ng AIM GLOBAL, marami na ang napapagaling at nadugtungan ng buhay…at Syempre hindi rin po mawawala ang panalangin at pananalig sa ating POONG MAYKAPAL.😇🙏 Huwag nyo na pong hintayin ng may mangyari hindi maganda sa inyo bago pa kayo kumilos...JOIN NA RIN KAYO PARA MASUBUKAN NYO NA RIN kung Gaano ka GALING ANG AIM GLOBAL PRODUCT... . Glory to God dahil may bagong Buhay na naman ang natulungan sana kung nalaman din agad na may ganito na paraan na hindi rin basta basta maniniwala sa ibang sasabihin ng Dr.hindi naman lahat pero operation is not easy but easy money,buti nalang at merong ganitong mga amazing products na makakatulong sa tao na may sakit .... Kaibigan... kung may kakakilala kayo na may mga sakit share nyo lang din sa kanila. Super Effective Products pm sa mga oorder po. #HealthIsWealth #TheBestProducts #AimazingAimProducts #AmazingC24/7 If you really CARE! Please👍Like 🗨️comment 🔖tag ↪️share It may SAVES someone LIFE😍 ORDER NOW ➤ ➤ bit.ly/MjC247 CASH ON DELIVERY ➤ ➤ bit.ly/MjC247 To know more about c24/7, click here➤ ➤ http://m.me/amazingC24

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iwantthis-c247 · 6 years ago

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C24/7 Membership: Purchase 1 set of C24/7 Mega Package from Amman, JORDAN

#TodaysTransaction #MembershipPurchase 🛫 Ship Bound to AMMAN, JORDAN Got another membership, 1 set of#C247FoodSupplement MegaPackage, purchasing by Brother Mohd from (Amman, Jordan) and received payment via #WesternUnion. Thank you so much for trust us! Until next order transaction! Thankyou! ★ www.c247foodsupplement.com 👈 ★ www.fb.com/Share.C247 👈 67 • 07/17/2018 #HealthConcern: #ReceivedPayment: Western Union #FreeShipping: thru #DHLExpress #DoorToDoorDelivery #Amman #Jordan #LookingForOverallHealth? 👌 Interested orders: 📱Contact us at: Direct Call: (+63) 09398538184 Viber/WhatsApp: +639154267370 Message us: m.me/Share.C247 Email us: [email protected] 📩 Send PM @ fb.com/Share.C247 🛒 http://buy.c247.today/ #C247 #FoodSupplement #AntiOxidant#OverallHealth #GoodForHealth#BreakthroughProduct #ProductOrder#C247FoodSupplement #HerbalSupplement#C247Naturaceutical #AmazingProduct

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manglayangseo · 7 years ago

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Propolis Moment Tokopedia Di Bandung Hubungi No. WA : 0818-0986-7604

New Post has been published on http://ubpreneur.com/propolis-moment-tokopedia-di-bandung.php

Propolis Moment Tokopedia Di Bandung Hubungi No. WA : 0818-0986-7604

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amcrasto · 7 years ago

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Persulfurated Coronene: A New Generation of “Sulflower”

2073844-77-4 C24 S12, 673.04 Coroneno[1,12-cd:2,3-c‘d‘:4,5-c”d”:6,7-c”’d”’:8,9-c””d””:10,11-c””’d””’]hexakis[1,2]dithiole

A persulfurated coronene, a molecule dubbed a “sulflower” for its resemblance to a sunflower, bloomed this year. It’s the first fully sulfur-substituted polycyclic aromatic hydrocarbon and only the second member of a new class of circular heterocyclic…

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#SUNFLOWER

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blogrevolve2020 · 4 years ago

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The Winners of the 2009-20 SBB Grant Program

Chicago-based investment firm SBB Research Group applauds the August 5th finalists of its own month-long grant program aiding impactful non-profit organizations during the 2009-20 pandemic season. This year's awardees (listed below in alphabetical order) offer a variety of solutions to the greater Chicago area: C24/7 (Chicago), the Center for Social Inclusion (wrigleyville, IL), Illinois AIDS Society (Champaign), and National AIDS Memorial Foundation (Chicago). Other members of this SBB Research team are also responsible for providing services for other members of the Chicagoland area.

The middle for Social Inclusion is known as a community source for various social service providers, including social workers, counselors, lawyers, etc.. Its program provides free assistance to people with HIV and AIDS and their families that are at risk of losing job or facing discrimination from businesses SBB Research Group. The Center also works to reduce poverty through access to financial aid.

The HIV/AIDS App of SBB Research provides financial aid to people with HIV that are employed in Champaign and different regions of the state. Funding is available for somebody to help cover his or her HIV medical bills, as well as help pay for housing, transportation, and food. An individual might also be eligible to receive other benefits such as free clothes, or food vouchers for food pantries.

The middle for Social Inclusion's HIV/AIDS Outreach Team provides outreach programs to your local healthcare provider that offers care for people with HIV. The outreach team, called the"Social Impact Team," has worked with this health care provider to execute a multifaceted, strategic approach to AIDS education and outreach. Through such efforts, the medical care provider provides education to its customers about the disease, its prevention, its symptoms, and HIV therapy. The program also offers free screenings, free counselling and referral services, and free food vouchers to the food pantry of the neighborhood gym. As a result of this work, the social support supplier is able to serve an increased variety of people, making it simpler for them to provide improved service to their clientele.

The Illinois AIDS Society is a nonprofit company whose main mission is to enhance the quality of life of individuals living with HIV and AIDS. It works to increase awareness, encourage, and tools for people living with the illness. The AIDS Society also works to enhance the standard of life by helping to avoid illness and increase awareness about the disease among vulnerable communities.

The AIDS Society is located in Champaign, IL and serves families and individuals living with HIV or AIDS, the elderly, children, and people with disabilities. The organization is committed to improving the lives of those it serves through educational programs, HIV/AIDS prevention, public awareness, fundraising, and advocacy, and support solutions.

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pusongbigo · 7 years ago

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Start a global business with our low-cost business starter package. This is can be the start of your Multi-million Business Venture. Package Includes: 4 C24/7 BP's 2 Careleaf Packs ADDITIONAL INFORMATION BUSINESS KIT Start-up sales kit: Folder for presentationVideo Presentation CDInsurance CertificateScholarship CertificateATM application form (BPI Globe BanKO)ID application form ATM REGISTRATION FORM The ATM will be used for your daily and monthly income. WEBSITE/WEBPAGE Your own account in AIM Global’s computer system that monitors all your and your group’s successful sales transactions. TECHNOLOGY SERVICES Real-time internet-based access to your account 24/7. All members enjoy the following benefits: DISCOUNTS Enjoy 25% lifetime discounts on all AIM Global’s Products. PERSONAL ACCIDENT INSURANCE (by Prudential Guarantee) Php 200,000 – Accident InsurancePhp 50,000 – Unprovoked Murder and AssaultPhp 10,000 – Medical ReimbursementPhp 10,000 – Burial Assistance FREE MEDICAL CHECK UP TRANSFERABLE SCHOLARSHIP Choose from our 300+ affiliated schools nationwide! This scholarship program may be given to anyone you know. GLOBAL BUSINESS Enjoy the privilege of being an independent distributor and have your own GLOBAL BUSINESS with six (6) major ways to earn through the AIM Global International Expansion Program. #If you interested send messege ask me how...:) #aimjha #aimers #aimhigh #aimglobalworks #aimglobalproducts

#aimglobalproducts #aimhigh #aimglobalworks #if #aimers #aimjha

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abundanceely-blog · 7 years ago

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#C247ProductTestimony #C247 #C247ShareTestimony #C247Repost THE AMAZING HEALING POWER OF C24/7! Hello po sa lahat ako po si Cristina Belmonte taga Bulacan. Ako po ay may goiter dati na naka-schedule ng operahan,sa tulong ng aming pamangkin na si Rowena Medina na isang member ng Alliance in Motion Global ipinanainom niya sken ang C24/7 noong October 2016 na product ng Aim Global sa una tumanggi talaga ako kasi hindi ko kilala yung gamot.mabuti nalang at kinulit ako ni pamangkin na subukan ko nga daw itong C24/7 inumin wala naman mawawala sken kapag ininom ko,samakatuwid ininom ko ito, sa pag-inom ko ng C24/7 isang buwan palang akong umiinom nahahalata ko na lumiliit ang goiter ko, ang sabi ko pa sa pamangkin ko "wow totoo nga mabisa ang C24/7" sa kaya tinuloy-tuloy ko itong inumin hanggang sa ngayon magtatatlong buwan palang akong umiinom ng C24/7 ang bilis ng pagbabago.Samahan mo ng Panalangin sa Panginoong Diyos sigurado kahit ikaw na umiinom nito magugulat sa bilis ng paggaling mo.salamat sa Diyos kasi nakilala ko ang Aim Global na siyang naging susi para akoy gumaling.ako ngayoy member na ng Aim Global sobrang napakagaling ng aming mga product ako na po mismo ang nagpapatunay nito.

SHARE IF YOU CARE!!! * 100 USES OF C24/7 Here under is the list of 100 diseases that C24/7 Natura-ceutical can help remedy, through providing the daily essentials, anti-oxidants and other nutrients the body needs on a daily basis. To learn more about the disease: Acute and Chronic Diarrhea Allergic Rhinitis Amenorrhea Anemia Atomic Dermatitis Atrophic Vaginitis Benign Prostatic Hypertrophy Beri-beri Bone Fracture Brain Tumor Bronchial Asthma Bronchitis Burns Cancer and Tumor Formation Cataract Cervical Ulcer Choletithiasis-Gallstones Colitis Colon Prolapsed and Bowel Pockets Conjunctivitis Constipation Cough Cyst Deafness of Old Age Diabetes-Insulin Dependent Type I Diabetes Mellitus Type II Dysmenorrhea Dyspesia Ecopora Edema Endometriosis Enteritis -Swelling of Intestines Epilepsy Gastro-Esophageal Reflux Disease (G E R D) Gingivitis Glaucoma Goiter Gout Halitosis Heart Disease and Complication Hepatitis Hypercholesteolemia Hyperlipidemia Hypertension Immunodeficiency Insomnia Kidney Disease Laryngitis Leucorrhea Liver Cirrhosis Low Sperm Count Mascular Degeneration Mental Tiredness Migraine Muscle and Nerve Pain Muscular Dystrophy Myoma Nephrolithasis Neuralgia Neuro Muscular Disorder Osteoarthritis Osteoporosis Pancreatitis Paralysis Parasistism Patients with Debilitating Disease Pharyngitis Piles – External Swelling Piles After Operation Pre Menopausal Syndrome Prolapse of the Stomach Psoriasis Rectal Tumor Respiratory Infection Rheumatic Heart Disease Rheumatoid Arthritis Scurvy Shortness of Breath on Children Sinusitis Skin Rash Skin Ulcer Sore Eyes Spinal Disease Stroke Systemic Lupus Erthromatosis Tendonitis Thrombosis Thyroid Problem Tinnitus Tonsilitis Toxic Blood and Acidosis Toxins in the Body Trochomonas Vaginilis Ulcer Colitis Underweight and Malnutrition Urethritis Vaginitis Varicose Veins Vertigo Weakness of Lower Leg Anyone who's looking for in good health and to get rid of those diseases especially whose suffering by any formation of cancer disease)!!!#PreventANYdiseases Try and take the C24/7 Naturaceutical Food Supplement, the all-in-one food supplement that eliminates all kinds of diseases from cough, flu, asthma, myoma, arthritis, up to cancer, in just one capsule of C24/7 that consists of 22,000 phyto-nutrients & antioxidants (plant & herbal derived)!!! Always remember: Health is Wealth! It's better to prevent than cure!!! #TakeC247Now! √ PLEASE SHARE & TAGGED THIS POST IF YOU REALLY CARE YOUR LOVED ONES, YOU ALREADY KNOW THEY'RE SUFFERING IN HEALTH! SHARING IS CARING!! 👌 Interested orders: 📱Contact us at: Direct Call: (+63) 0939391588998 Viber/WhatsApp: +639272813925 Message us: https://goo.gl/BciHJh Email us: [email protected] 📩 Send PM @ https://goo.gl/RZKLWY #HealthConcern: Maintenance #ReceivedPayment: Remitly (BDO) #EMSExpress #California #USA #LookingForOverallHealth?

#AimGlobal #C24/7 #HealthIsWealth #HealthAwareness #Naturaceuticals #foodsupplement #OnlineBusiness #BusinessIdeal

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nofomoartworld · 7 years ago

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Art F City: This Week’s Must-See Art Events: Virtual Reality Exhibitions and Cyberdefense Workshops

The tight stuff and the right stuff at tonight’s special event with @babycastles –@di_mo_da @micahnotfound @moisesnotfound @akaprash @princessgollum and many more superstars 7-10pm Only @vrworldnyc #virtuallyexcited #actuallyexcited

A post shared by madabouteug (@madabouteug) on Jul 17, 2017 at 2:51pm PDT

Well, this week starts off strong. Monday we’re looking forward to checking out the new VR World NYC, which is hosting a virtual reality art show and concert until midnight. If that hasn’t sated your cyberpunk hunger, check out Lin Wang’s cyborg wigs tuesday at Gallery Sensei, the NYFA/NYSCA group show Facial Profiling at C24 Gallery on Thursday, or the “Digital Self Defense and Empowerment Workshops” happening all Saturday afternoon at the New Museum. We love when a week’s itinerary in IRL New York looks like a montage from Hackers.

Mon

VR World NYC

4 East 34th Street New York, NY 7:00 p.m. - 12:00 p.m. Website

Virtual Insanity™: VR + Music

Well this is undoubtedly the coolest thing happening on a Monday night this summer. Babycastles is presenting a virtual reality art show and concert at VR World NYC.

Among the highlights is the Digital Museum of Digital Art, which Paddy and I have both experienced and raved about. It’s seriously one of the best art-viewing experiences you can have this week, so get yourself there ASAP.

Artists: Alfredo Salazar-Caro and his virtual institution Di Mo DA, Art 404, Haleek Maul, James Orlando, HYPER.ZONE, LaJuné McMillian, Michelle Cortese, Michelle Senteio, Nicole Ruggiero, Prashast Thapan

Live performances by: Icarus Moth, RAFiA, Haleek Maul

Tue

Gallery Sensei

135 Eldridge Street New York, NY 6:00 p.m. - 8:00 p.m. Website

Lin Wang: Tenant, Tranant, Trance

This show is only up for two days, a unusual duration for an installation that has to do, on some level, with time. Lin Wang’s semi-narrative installation alludes to past tenants of a surreal domestic space, which itself is somewhat anachronistic—referencing a cyborg future where the synthetic and prosthetic wait to merge with absent bodies. The artist has created a series of household appliances associated with comfort (fans, massage chairs, etc.) combined with wigs. Picture mounds of artificial hair quivering in anticipation of contact with a user. So creepy, yet so alluring.

Artists Space

55 Walker Street New York, NY 7:00 p.m. - 9:30 p.m. Website

People's Cultural Plan Launch

This looks good: Mychal Johnson, community activist and member of South Bronx Unite, and artist Chloë Bass will discuss the ins and outs of the People’s Cultural Plan. It’s a grass-roots, social-justice focused alternative to the Department of Cultural Affairs’ CreateNYC plan, which launches this week. The guiding principles here are de-gentrification, cultural equity, and labor equity—three things the city desperately needs, in particular for the survival of the arts.

The event features drinks, opportunities for discussion and mingling, and translators in Chinese and Spanish. This is a great opportunity to meet other artists thinking politically and getting involved in the interrelated labor/gentrification struggles happening now in New York.

Wed

Equity Gallery

245 Broome Street New York, NY 6:00 p.m. - 8:00 p.m. Website

Liana Finck: Passing for Human

Liana Finck is the most millennial comic artist I can think of for several reasons. For one, her pen-and-ink melancholic musings on relationships, existential angst, and the never-ending stresses of being a broke 20-something are relatable and often hilarious. Also, she’s built her fan base out of her popular Instagram account. Here’s a chance to see her work (some 80 drawings!) IRL.

EFA Project Space

323 West 39th Street New York, NY 7:00 p.m. - 8:30 p.m.Website

Setting 1880-1920 / Dinner Party

Liliana Dirks-Goodman’s theatrical dinner party/lecture/performance will introduce guests to “the utopian design visions of seven first-wave white feminists” who lived in the decades surrounding the turn of the last century. This is the era when a lot of social “progressives” advocated for urban planning, design, and architectural movements intended to better the lives of the poor and immigrants. We often hear about men’s grand visions for the “city beautiful” or Garden City movements, but the fact that many of these visionaries and activists were women is often overlooked. Their different perspective was often aimed at improving the lives of women as well.

The dinner (arguably the most highly-gendered domestic social activity of the 20th Century) will be prepared by chef Kristin Worral, who will use recipes from Rumford Kitchen’s cookbook.

Thu

167 Canal Street, 5th floor New York, NY 6:00 p.m. - 9:00 p.m. Website

My fossil, my echo / my excess, my scrap

This exhibition is curated around the idea of anxieties related to the index. The curatorial statement, from Gabrielle Jensen and Julia Lee, is a bit dense, but the show looks really promising. Chiefly, the concern here seems to be what becomes of an object once it is a record or fragment of itself?

I’m excited to see Carmen Neely included in this exhibition. When I met her on a studio visit years ago I was convinced she’d be an art star. Her work includes personified abstract forms that jump from piece to piece, personal objects embedded in canvases, and plenty of autobiographical ephemera worked into painterly compositions. It definitely fossilizes some weird stuff, and does it charmingly.

Artists: Cristine Brache, Isabel Legate, Carmen Neely, Kayode Ojo, Patrice Renee Washington

C24 Gallery

560 West 24th Street New York, NY 6:30 p.m. - 8:30 p.m. Website

Facial Profiling

Curated by David C. Terry, this show looks at identity through the lens of seven NYSCA/NYFA Artists. The artists here touch on issues such as “the observed self, the portrayal of individuals as well as the perceived and projected self, and how we interpret/project imagery as portrait.” Included among the seven is master of selfies/constructed identity Sean Fader, so expect there to be a dash of humor among what could otherwise be heady navel gazing.

Artists: Samira Abbassy, Kwesi Abbensetts, Geoffrey Chadsey, Sean Fader, Michael Ferris Jr. , Kymia Nawabi, Oliver Wasow

Sat

New Museum

235 Bowery New York, NY 1:30 p.m. - 6:00 p.m. Website

Digital Self-Defense and Empowerment Workshops

In conjunction with the exhibition Paul Ramírez Jonas: Half-Truths, the New Museum has teamed up with Equality Labs and NEW INC residents DATA X and Taeyoon Choi to offer an afternoon of workshops about surveillance and autonomy in the digital age. So spend a muggy Saturday nerding out to all your hacker fantasies in the New Museum’s air conditioning.

Here’s the rundown of workshops:

1:30 p.m. – 3:00 p.m. Handmade Computers with Taeyoon Choi—learn how to assemble a basic computer that can perform addition, keep time, and store memory! It’s free, but requires registration by emailing [email protected] .

3:15 p.m. – 4:00 p.m. Data Selfie with DATA X—DATA X is a creative studio that believes in transparency. Here, they’ll be demonstrating their browser add-on Data Selfie, which tracks the way sites such as Facebook track your data, giving the user a peak at how corporations and their algorithms view us. Register here.

4:00 p.m. – 6:00 p.m. Digital Self-Defense with Equality Labs—Equality Labs, “a South Asian women’s, gender non-conforming, and trans tech collective” will present a workshop about protecting one’s information in the age of the surveillance state. This is pretty useful stuff as the world becomes more and more like William Gibson’s worst authoritarian nightmare. The event is limited to 30 participants, so be sure to register here ASAP.

Pine Box Rock Shop

12 Grattan St Brooklyn, NY 2:00 p.m. - 6:00 p.m. Website

Meowmania! A Cat Party in Brooklyn

It is Summer in New York City, which means our art event guides tend to be a little heavier on events that are just ridiculous or activism-oriented than usual due to the dearth of art openings. This event is both.

Bring your leashed cat to partake in activities such as a cat photobooth, games, cat-themed drink specials, and a cat costume contest. The whole event is a fundraiser for local cat rescue programs, so all of this “basically internet circa 2012” style shenanigans is at least for a good cause.

Sun

Brooklyn Museum

200 Eastern Parkway Brooklyn, NY 1:00 p.m. - 3:00 p.m. Website

Performance in the Park: Maren Hassinger's "Pink Trash"

As part of the Brooklyn Museum’s exhibition We Wanted a Revolution: Black Radical Women, 1965–85, Maren Hassinger will be re-staging her 1982 performance “Pink Trash” in Prospect Park. The piece was an important reflection on public space, labor, and “maintenance art”, and seeing it performed three decades later is bound to be something special.

Tickets are $25, but you get a lot of bang for your buck:

1:00 p.m. Special tour of We Wanted a Revolution and conversation with co-curator Rujeko Hockley and Maren Hassinger

2:00 p.m. Walk to Prospect Park

2:15 p.m. Performance of “Pink Trash”

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