|Publication number||US5037795 A|
|Application number||US 07/265,244|
|Publication date||Aug 6, 1991|
|Filing date||Oct 31, 1988|
|Priority date||Mar 9, 1987|
|Publication number||07265244, 265244, US 5037795 A, US 5037795A, US-A-5037795, US5037795 A, US5037795A|
|Inventors||Larry F. Wieserman, Karl Wefers, Kathryn Cross, Edward S. Martin|
|Original Assignee||Aluminum Company Of America|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (11), Referenced by (17), Classifications (22), Legal Events (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. Ser. No. 023,423, filed Mar. 9, 1987, now U.S. Pat. No. 4,788,176, which is a continuation-in-part of U.S. Ser. No. 946,870, filed Dec. 29, 1986 (now abandoned), and is related to U.S. Ser. No. 023,312, filed Mar. 9, 1987, now U.S. Pat. No. 4,871,711 and U.S. Ser. No. 023,429, filed Mar. 9, 1987, now U.S. Pat. No. 4,786,628.
1. Field of the Invention
This invention relates to improved chromatography packing material. More particularly, this invention relates to such a packing material comprising a generally spherical metal oxide/hydroxide particle comprised of solid crystals of metal oxide/hydroxide, with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar, and having the surface thereof reacted with a phosphorus-containing material to form a layer thereon thereby to provide an improved chromatographic packing material.
2. Description of the Related Art
Chromatographic packing materials made from organic resins suffer from poor physical strength, poor thermal stability, high cost, solvent swelling, and low capacity. Chromatographic packing materials made from metal oxides such as silica exhibit poor chemical stability at high pH. For many applications, in particular for reversed phase chromatography, a chromatographic packing material with high physical integrity, good chemical stability over high and low pH conditions, specific surface functionalities, good thermal stability, and low cost is needed.
Other metal oxides such as alumina have been used as adsorbents because of the good physical integrity and low cost of alumina. The solubility of alumina in pH ranges between 4 and 9 is very low and the material is, therefore, chemically and physically stable in this pH range. However, beyond this pH range, on either the basic or acidic side, alumina becomes soluble in aqueous media and its physical strength and integrity degrades rapidly.
Modifications of metal oxide/hydroxide materials have been proposed. Wieserman et al U.S. patent application Ser. Nos. 946,870 and 023,423 disclose and claim metal oxide/hydroxide surfaces reacted with phosphonic acid or phosphinic acid to form a monomolecular layer thereon to stabilize the metal oxide/hydroxide by modifying the surface of the particle. Wieserman et al U.S. patent application Ser. No. 023,429 (U.S. Pat. No. 4,786,628) discloses and claims a chromatographic packing material comprising a metal oxide/hydroxide particle reacted with phosphonic acid to form a monomolecular layer thereon which provides a chromatographic packing material having good pH stability as well as high efficiency.
Martin et al U.S. patent application Ser. No. 023,312 discloses and claims the formation, on a metal oxide/hydroxide surface such as an aluminum oxide/hydroxide, of a monomolecular layer of a phosphorus-containing organic material having 1-2 phosphorus groups thereon. The phosphorus-containing groups described therein may comprise phosphoric acid monoesters or diesters.
Wilhelmy U.S. patent application Ser. Nos. 940,354 and 022,735 disclose and claim the formation of an aluminum hydroxide particle of extended area which comprises a generally spherical aluminum hydroxide particle comprised of solid crystals of aluminum hydroxide with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar.
Venables et al U.S. Pat. No. 4,308,079 teaches the treatment of an aluminum oxide surface of an aluminum substrate with a monomolecular layer of an amino phosphonate compound such as nitrilotris (methylene) triphosphonic acid to retard hydration of the aluminum oxide to aluminum hydroxide to provide a more stable microporous surface which is particularly suited to commercial adhesives. The presence of the hydrated oxide is said to interfere with the formation of a satisfactory bond between the adhesive and the oxide, while the phosphonate treatment is said to inhibit the conversion of the oxide to hydroxide without interfering with subsequent bonding of the adhesive to the oxide.
An improved chromatographic packing material is provided comprising a metal oxide/hydroxide particle having an extended surface area and a lower resistance to flow through the packing material and having on the surface thereof a layer formed by treating the surface of the support material with a phosphorus-containing material with the active or desirable remainder of the respective molecules forming the layer being oriented away from the surface of the metal oxide/hydroxide particle for interaction with organic materials being passed through the chromatography packing material.
It is, therefore, an object of this invention to provide an improved chromatographic packing material comprising a metal oxide/hydroxide particle of extended area with a layer of one or more phosphorus-containing materials on the surface of a metal oxide/hydroxide particle.
It is another object of this invention to provide an improved chromatographic packing material comprising a metal oxide/hydroxide particle of extended area with a layer of one or more phosphorus-containing materials bonded to the surface of a metal oxide/hydroxide particle to provide an improved chromatographic packing material having an extended surface area, lower resistance to flow through, stable at extended pH ranges, and capable of high efficiency in separation of materials.
It is still another object of this invention to provide an improved chromatographic packing material comprising a metal oxide/hydroxide particle of extended area comprised of solid crystals of metal oxide/hydroxide, with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar, with a layer of one or more phosphorus-containing materials reacted with the surface of the metal oxide/hydroxide particle to provide an improved chromatographic packing material having an extended surface area, improved chemical stability, and lower resistance to flow through.
It is a further object of this invention to provide an improved chromatographic packing material comprising an aluminum hydroxide particle of extended area comprised of solid crystals of aluminum hydroxide, with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar, with a monomolecular layer of one or more phosphorus-containing materials reacted with the surface of the aluminum hydroxide particle to provide an improved chromatographic packing material having an extended surface area, improved chemical stability, and lower resistance to flow through.
It is yet another object of this invention to provide a process for making such an improved chromatographic packing material.
These and other objects of this invention will be obvious from the following description and accompanying drawings.
FIG. 1 is a flow sheet illustrating the process of the invention.
FIG. 2 is an illustration of a two dimension crystal showing the effect of slower growing planes on the eventual habit or morphology of the crystal.
FIG. 3 is a graph showing the effect of sodium hydroxide concentration on the particle diameter to length ratio of sodium aluminate solutions aged at 75° C.
FIG. 4 is a graph of particle diameter to length ratio of sodium aluminate solutions aged at 75° C. at several sodium hydroxide concentrations as a function of methanol concentration.
FIG. 5 is a plot showing the predicted isomorphs as a function of sodium hydroxide and methanol concentrations.
FIGS. 6a is a scanning electron micrograph showing acicular aluminum hydroxide crystals.
FIGS. 6b is a scanning electron micrograph showing a generally spherical aluminum hydroxide particle comprising the acicular aluminum hydroxide crystals of FIG. 6a bonded together at a central core region.
FIGS. 6c is a scanning electron micrograph showing lamellar aluminum hydroxide crystals.
FIGS. 6d is a scanning electron micrograph showing generally spherical aluminum hydroxide particles comprising the lamellar aluminum hydroxide crystals of FIG. 6c bonded together at a central core region.
FIG. 7 is an illustration of the manner in which the phosphorus-containing group bonds to the metal oxide/hydroxide surface with the organic portion of the molecule facing away from the metal oxide/hydroxide surface.
FIG. 8 is a graph showing a comparison of the back-pressure for chromatographic columns respectively packed with the chromatographic material of the invention and prior art packing material.
FIGS. 9a-9e are chromatograms showing the separations of theophylline, p-nitroaniline, methyl benzoate, phenetole, and o-xylene eluted with solvents ranging in pH from 1 to 11 using the chromatographic material of the invention.
FIGS. 10a-10c are chromatograms showing the separation of an amine mixture of aniline, N-methyl aniline, and N,N-dimethyl aniline eluted with solvents ranging in pH from 7 to 11 using the chromatographic material of the invention.
FIG. 11 is a chromatogram showing the separation of a peptide mixture of methionine enkephalin and leucine enkephalin using the chromatographic material of the invention.
In accordance with the invention, the chromatographic packing material comprises a metal oxide/hydroxide particle of extended area comprised of solid crystals of the metal oxide/hydroxide, with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar, with a layer on the surface thereof comprising one or more phosphorus-containing materials. While the material of the invention as will be hereinafter described finds particular utility as an improved chromatographic packing material, it will be appreciated that the material may be used for other purposes as well such as, for example, a filler for polymers, a catalyst, catalyst support, flocculant, membrane coating, or for immobilizing bioactive materials such as enzymes.
The use of the term "metal oxide/hydroxide" herein is intended to define a broad spectrum of oxides ranging from those which may contain few hydroxides, e.g., activated forms of aluminum oxide (alumina) to more hydrated forms which may comprise mainly hydroxide, e.g., Al(OH)3. It has been found, however, that the metal with hydroxyl groups, rather than the metal oxide form without hydroxide groups, i.e., completely dehydroxylated forms, provides a better bond with the phosphorus-containing group on the molecule with which it is reacted. However, for certain applications, dehydrated or activated forms of the metal oxide/hydroxide may be preferred due to the higher surface area of such particles. For example, when an aluminum oxide/hydroxide is used, the hydrated form will be preferred, e.g., gibbsite, bayerite, or boehmite will be preferred when predominantly external surface and little or no internal surface area is desired, and activated alumina will be preferred when it is desirous that the metal oxide/hydroxide have a large internal surface area.
As presently understood, the metal oxide/hydroxides suitable for use in the present invention usually require hydroxyl groups on the surface thereof for purposes of providing bonding sites for the phosphorus-containing group or groups on the molecule to be chemically reacted or bonded to the metal oxide/hydroxide particle. For example, when the particulate material is alumina and the phosphorus-containing material is phosphonic acid, hydroxyl groups on the surface of the alumina are believed to react with the phosphorus-containing group of the phosphonic acid molecule, i.e., with the --POOH acid group of the phosphonic acid. When using an organic solvent, particularly where the solvent is immiscible with water,a monolayer of hydroxyl groups are provided on the alumina particles for purposes of reacting to form a chemical bond with the phosphonic acid groups. It will be appreciated that if more than a monolayer of hydroxyl units are present on the alumina surface, such as hydroxyl units present as a result of water, this additonal water layer can act to hinder the reaction. Thus, while it is preferred to have a maximum of a monolayer of hydroxyl units, less than a complete surface layer of hydroxyl units can be present on the metal oxide and such does not hinder reactivity.
While alumina, i.e, aluminum oxide/hydroxide, is a particularly preferred metal oxide/hydroxide support material for forming the chromatographic packing material of the invention, other metal oxide/hydroxides may also be used. Examples of such other metal oxide/hydroxides which may be used as the support particle for reaction with the phosphorus-containing material include any metal capable of forming an oxide/hydroxide selected form the class consisting of Groups IIIa (Sc and Y), IVa (Ti, Zr, and Hf), Va (V, Nb, and Ta), VIa (Cr, Mo, and W), VIIa (Mn, Tc, and Re), VIII (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt), Ib (Cu, Ag, and Au), IIb (Zn, Cd, and Hg), IIIb (B, Al, Ga, In, and Tl), IVb (Ge, Sn, and Pb), Vb (As, Sb and Bi), elemetns in the lanthanide series and the actinide series, mixtures thereof, and mixtures of Groups IIa (Be, Mg, Ca and Ra) and VIb (Se, Te, and Po) and combinations thereof. For example, the oxide/hydroxides of magnesium, titanium, zirconium, iron, chromium, zinc, vanadium, and combinations of these may be used. Particularly preferred metal oxide/hydroxides are the oxide/hydroxides of Al, Ti, Zr, and Fe.
Also, a core or center of iron oxide/hydroxide or other paramagnetic or ferromagnetic material may be used with a coating of a metal compound to take advantage of the magnetic properties of the iron oxide/hydroxide as an adsorbent. It should be noted that by use of the term "metal", it is intended to include not only the traditional metals, but also materials sometimes referred to as metalloids such as Se, B, As, and Te and to exclude the remaining elements referred to as nonmetals in the periodic table.
While the invention is primarily directed to the use of metal oxide/hydroxide particles as support materials for reaction with the phosphorus-containing organic molecules to form the chromatographic packing material of the invention, it is within the purview of this invention that other metal compounds could be used in substitution for the metal oxide/hydroxides such as metal silicates, oxalates, phosphates, sulfates, carbonates, apatites, hydrotalcites, zeolites, kaolin, clays and chromates as well as combinations of such materials or combinations of any of such materials with the preferred metal oxide/hydroxide support materials. Also metal oxide/hydroxides such as aluminum oxide/hydroxides with surfaces ion-exchanged or adsorbed with titanium, iron, or zirconium ions or oxides may be used.
The extended area metal oxide/hydroxide support particles may be formed in accordance with the teachings of the aforesaid Wilhelmy U.S. Pat. Applications (Ser. Nos. 940,354 and 022,735), now U.S. Pat. Nos. 4,900,537 and 4,822,593 cross reference to which is hereby made, to form the metal oxide/hydroxide particles of extended area which comprises a generally spherical particle comprised of solid crystals of metal oxide/hydroxide with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar.
The terms "particle morphology" and "habit" are synonymous with the shape or form of a crystal, e.g., lamellar, tabular, equant, columnar, or acicular, as opposed to the crystal structure or system, e.g., tetragonal, orthorhombic, monoclinic, etc. While the crystal structure determines the number and types of crystalline faces, the morphology or habit is determined by the relative growth rates of the crystalline faces, with the fastest growing faces "disappearing" leaving the slower growing faces to define the final shape.
This effect is shown in FIG. 2 with a two dimensional crystal where the (110) and (110) planes grow faster than the (100) and (010) planes. As seen in the outer edges of the illustrated crystal, the slower growing (100) and (010) planes then eventually define the habit or morphology of the crystal.
The Wilhelmy patent applications describe a process to control the morphology or habit of aluminum hydroxide crystals to permit the respective production of crystals which are principally lamellar (flat platelets) or principally acicular (needle-like) as well as intermediate forms.
As described therein, the aluminum hydroxide crystals may be precipitated from a caustic solution of alkali metal aluminate dissolved in an alkali metal hydroxide or the solution may be a so-called "Bayer liquor" produced in the caustic digest of an alumina-bearing ore such as bauxite by a caustic solution containing an alkali metal hydroxide such as sodium hydroxide in what is known as the "Bayer Process".
While the above description is particularly applicable to the formation of aluminum oxide/hydroxide particles which are generally spherical and comprise solid crystals of aluminum oxide/hydroxide, with the crystals extending radially outward from a central core region and having a shape selected from principally acicular to principally lamellar, other metal oxide/hydroxide particles in similar physical form may also be used as the support surface in forming the chromatographic packing material of the invention.
By use of the term "crystals" is meant a material or form having a particular morphology or habit, including an amorphous form, but not necessarily an ordered atomic structure or x-ray diffraction pattern.
To produce the chromatographic packing material comprising the metal oxide/hydroxide reacted with one or more types of phosphorus-containing organic molecules, the metal oxide/hydroxide, such as alumina, should first be activated or calcined. This calcination step increases the porosity and therefore the surface area of the metal oxide/hydroxide which, in turn, permits the formation of a higher weight percent of coating material to be applied. The calcination also causes any sodium remaining in the material to migrate to the surface where it can be removed as will be described below. The calcination can be accomplished by heating the metal oxide/hydroxide to a temperature of from about 300° to 1100° C., preferably about 500°-950° C., depending upon the particular metal oxide/hydroxide used, typically about 650°-950° C. for alumina, and maintaining the metal oxide/hydroxide at that temperature for about 1 to 10 hours, preferably about 2-3 hours. This activation is usually carried out at ambient pressure, but the use of higher or lower pressures is also possible.
The calcined or activated metal oxide/hydroxide should then be neutralized if any alkali metals are present in the starting materials. This may be accomplished by slurrying the metal oxide/hydroxide material in deionized water and holding the material in suspension by vigorous stirring, e.g., mechanical stirring, while the pH of the slurry is measured. An acid such as nitric acid may be added to the slurry until the pH reaches about 6.5. The slurry is maintained at this pH for about 2 hours after which the metal oxide/hydroxide may be allowed to settle. The liquid is then removed, e.g., by decanting, and then the product is further washed with deionized water. This wash water is then also removed from the metal oxide/hydroxide and the product is dried to remove any remaining wash liquid.
The calcined and neutralized metal oxide/hydroxide may then be reacted with a phosphorus-containing material such as a phosphoric acid monoester, a phosphoric acid diester, a phosphonic acid, or a phosphinic acid in a suitable media including an aqueous or nonaqueous solution, emulsion, or suspension, at a temperature which may range from just above the freezing point of the solution up to about the boiling point, typically from about 10° C. up to about 90° C., preferably about 50° C., for a period of from at least 0.01 second to not more than 20 hours, and preferably from at least about 0.5 hours up to about 4 hours, using an initial acid concentration of at least about 0.0001 to 0.1 molar. In some instances higher concentrations may be desired. When the media is non-aqueous, the temperature range can be greatly extended. For example, it may range from 5° C. or lower to 200° C. or sometimes higher depending on the solvent. The reaction is normally carried out at atmospheric pressure. However, the use of an elevated pressure or a subatmospheric pressure should be deemed to be within the scope of the invention. A flowing bed reactor or an aerosol may also be utilized in the treatment of the metal oxide/hydroxide particles with the phosphorus- containing material.
The formula for the phosphoric acid monoester useful in the practice of the invention may be written as (RO)PO(OH)2 while the phosphoric acid diester formula may be written as (RO)(R'O)PO(OH). The formula for the phosphonic acid useful in the practice of the invention may be written as RPO(OH)2 while the phosphinic acid may be written as RR'PO(OH).
In each instance, R' may be hydrogen and both R and R', when in monomeric form, may each be comprised of 1-30, but more typically 6-30, carbon-containing molecules such as an alkyl group. It will, however, be appreciated that the number of carbon atoms in the carbon-containing group may be as high as 5000 when polymeric carbon-containing groups are used, as will be discussed below.
Other examples of groups which may comprise R and/or R' include long and short chain aliphatic hydrocarbons, aromatic hydrocarbons, carboxylic acids, aldehydes, ketones, amines, amides, thioamides, imides, lactams, anilines, pyridines, piperidines, anhydrides, carbohydrates and thiocyanates, esters, lactones, ethers, alkenes, alkynes, alcohols, nitriles, oximes, organosilicones, sulfur containing organic compounds, ureas, thioureas, perfluoro organic molecules, perchloro organic molecules, perbromo organic molecules and combinations of these groups. The phosphorus-containing organic molecules such as listed above may also include inorganic groups substituted thereon such as halogens, nitrates, phosphates, phosphinates, phosphinites, phosphonates, quaternary ammonium salts, and the like. While it is preferred that the free end of the organic group extends away from the surface of the metal compound particle, it is within the scope of the present invention to provide, on the free end of the molecule, functional groups. Functional groups may be defined as the group on the molecule which enables the reactive material (comprising the phosphorous-containing organic material bonded to the metal oxide/hydroxide surface) to react with, attract, couple to, bond with, etc. other atoms, ions and/or molecules. By attaching specific functional groups, either organic or inorganic, to the R and R' groups of the phosphoric esters or the phosphonic and phosphinic acids, a wide variety of adsorbent selectivities and capacities are provided. such functional groups may be already attached to the R and/or R' groups of the phosphorus-containing material prior to reaction with the metal oxide/hydroxide surface or the R and/or R' groups may be modified after the reaction with the metal oxide/hydroxide surfaces.
The functional groups attached to or contained within the free end can be selected from cation exchange functional groups and anion exchange functional groups such as --SO3 H, --N+ (CH3)3 Cl, --COONa, --NH2 and --CN, for example. The --SO3 H functional group permits removal of cations such as Cu+2, Fe+2, Co+2, Cd+2, Ca+2, Sr+2, Hg+2, Pb+2, Ba+2 and Be+2 from aqueous media. The functional group, --CH2 N(CH3)3 Cl, permits removal of anions such as HSO4 --, ClO3 --, NO3 --, NO2 --, HPO4 --, formate, and citrate. Other examples of functional groups that may terminate the free end of the phosphonated bonded hydrocarbon chain include the following: a carboxyl group, e.g., a carboxymethyl group, a glucose group, a monoclonal antibody, a cyano group, a phenyl group, a diphenyl group, a tertiary butyl group, a sulfonic group, a benzyl sulfonic group, protein groups such as protein A (staphytococcal protein A), enzyme groups, dye molecules, chelated metal groups, tag molecules and combination of these groups. Further, it should be noted that the carbon group can be a saturated or unsaturated carbon chain, cyclic group, polyaromatic group, or heterocyclic group.
The coated surface may also be further modified by materials which do not actually form a chemical bond with the phosphorus-containing organic acid bonded to the surface of the metal oxide/hydroxide. For example, a solution of a material such as 1-octadecyl sulfonic acid could be flowed over an active material already formed in accordance with the invention comprising a generally spherical particulate metal oxide/ hydroxide reacted with a phosphorus-containing organic acid. The non-polar end of the sulfonic acid molecule would intercalate with the hydrophobic phosphorus-containing organic acid layer on the spherical metal oxide/hydroxide particle, but would not form a chemical bond with the phosphorus-containing organic acid. This is a means for immobilizing specific functional groups on the hydrophobic surface without chemically bonding them to the surface.
It should be noted that the R or R' groups may be monomers or may be oligomers or polymers. Preferably, the oligomers have a molecular weight of less than 2000, while the polymers may have a much higher molecular weight, e.g., as high as 60,000 with as many as 5000 carbon atoms, i.e., a high polymer or macromolecule. By the use of monomer herein is meant to include a chemical compound that can undergo polymerization. By oligomer is meant a polymer or polymer intermediate containing relatively few structural units, i.e., a polymer containing 2-4 monomers. It must be further noted that the resultant material which is useful in forming the product of the invention is a polymer which has been reacted with a phosphorus-containing material, in contrast to a polymerized monomer with repeating phosphorus-containing groups.
While we do not wish to be bound by any particular theory of bonding, it is believed that when a metal oxide/hydroxide particle, for example, alumina, is brought into contact with the phosphorus-containing molecule, e.g., phosphoric acid mono or diester, phosphonic acid, or phosphinic acid, a reaction or adsorption of the phosphorus-containing group on the alumina takes place in which the aluminum and phosphorus atoms in the respective molecules are apparently bonded together through an oxygen atom as illustrated in the formulas below: ##STR1##
Thus it can be seen, using the above proposed models, that if all of the exposed hydroxyl groups on the surface of the metal oxide/hydroxide can be reacted with the phosphorus containing groups of the respective molecules, the surface chemistry of the reacted metal oxide/hydroxide will be changed.
Furthermore, the type of organic radical attached to the phosphorus-containing group or groups can be tailored to achieve certain types of affinities to provide selectivity in the adsorption characteristics of the product. For example, when an alumina treated with a phosphonic or phosphinic acid having a octadecyl R group is used, the following type of selectivity can be achieved. For example, theophylline, p-nitroaniline, methyl benzoate, phenetole, and o-xylene under chromatographic conditions can be selectively separated by adsorption on such a reactive material in accordance with the present invention, as shown in the chromatograms of FIGS. 9a-9e. This is because the retention time increases with decreasing effective polarity or charge.
The chemical bonding of the phosphorus-containing molecule, such as the phosphoric esters or the phosphonic or phosphinic acids, to the metal oxide/hydroxide particle, e.g. alumina particle, is illustrated in FIG. 7 wherein, for illustrative purposes only, the metal oxide/hydroxide surface is shown as completely spherical having a surface 50. The phosphorus-containing organic molecule is chemically bonded at one end to surface 50 by means of a phosphorus-oxygen-metal bond. As presently understood, it is preferred that the other or free end of the phosphorus-containing organic molecule extends away from the surface of the particle, as shown in FIG. 7. Further, it is important to control the application or bonding of the phosphorus-containing molecule to the metal oxide/hydroxide support when it is desired to obtain a monomolecular layer bonded to the metal oxide/hydroxide particle as illustrated in FIG. 7.
It should be noted that while the chemical bonding of the phosphorous-containing material to the metal oxide/hydroxide surface to form a monomolecular layer in one embodiment is preferred, physical adsorption of the phosphorus-containing material is also within the purview of the invention as well as, in certain circumstances, the formation of multiple layers of the phosphorus-containing material on the metal oxide/hydroxide particle surfaces.
By "monomolecular layer" is meant that 90%, and preferably 98%, of the phosphorus-containing organic molecules are bonded to the metal oxide/hydroxide particle surfaces as a single layer of molecules. Thus, the application should be controlled so as to prevent the R or R' groups from bonding to each other to form weakly adsorbed multilayers which would then provide further hydroxyl units, i.e., --POOH units directed away from and not bonded to the surface of the metal oxide/hydroxide particles, thereby defeating the purpose of the invention, for example, when it is used for an adsorbent. The thickness of the phosphorus-containing bonded organic monolayer is in the range of 3 to 5000 Angstroms and preferably 5 to 500 Angstroms.
The presence of a monomolecular layer may be determined using solids NMR (nuclear magnetic resonance) techniques using 31p isotopes.
It should be further noted that the formation of the monomolecular layer of the phosphorus-containing organic molecules on the metal oxide/hydroxide surface should react with substantially all of the reactable hydroxyl groups on the surface of the metal oxide/hydroxide support to ensure that materials subsequently adsorbed on the surface are not bound to unreacted hydroxyl groups on the support material but rather are adsorbed onto the altered surface, i.e., adsorbed onto the organic end of the phosphorus-containing organic molecules bonded to the surface of the support material. By the term "substantially all" of the reactable hydroxyl groups on the metal oxide/hydroxide support is meant that at least 90%, preferably at least 99%, and most preferably over 99% of the hydroxyl groups are reacted with the phosphorus-containing organic molecules.
It is preferred that the monomer or oligomer used is at least a five or six-carbon chain. The chain can have 20 to 30 or more carbons, as noted earlier, when R or R' is a monomer, and as much as 5000 carbons when a polymer is used as R or R'. The longer chains preferably are used in the in:tial bonding or loading of the metal oxide particle w:th the phosphorus-containing carbon material. However, in some instances, because of the pores and fisures that can be present on the metal oxide/hydroxide particle, particularly those having high surface area, sometimes all the surface hydroxyl units are not reacted because of the inability of the longer chain phosphorus-containing organic material reaching or diffusing into the pores and fissures. Thus, if it is desired to inert or block such remaining reactive sites, short-chain monomers or oligomers, e.g., less than 6 carbon molecules per chain, may be used. In this way, when necessary, all of the reactive sites may be capped or blocked. That is, for capping off the reactive sites, short-chain monomers can be used.
Thus, for example, if desired, an alumina treated with a high molecular weight phosphonic or phosphinic acid, e.g. an n-heptadecylphosphonic acid, may be further treated with a low molecular weight phosphonic acid, e.g., methylphosphonic acid, to treat any remaining unreacted alumina surface areas.
The available surface area, both outside and inside of the pores, will be somewhat dependent upon the relationship between the pore size of the metal oxide/hydroxide support material and the length of the R group on the phosphorus-containing molecule. If the pore size is small with respect to the size of the R group on the phosphorus-containing molecule, the phosphorus-containing group may or may not be able to enter into the pores, thereby changing the effective area available for interaction with the organic material being passed through the chromatographic column.
The weight of the layer of phosphorus-containing material can range from about 0.01 to 75 wt. % calculated on the total weight of the coated metal oxide, and preferably the layer can range from about 0.5 to 20 wt. %, typically 1 to 20 wt. %. For purposes of ensuring that a monomolecular layer of phosphorus-containing organic material is bonded to the metal oxide particles, when such is desired, the application should be carefully controlled. That is, a monomolecular layer can be obtained, for example, by controlling the viscosity of the aqueous medium of solution, the time of exposure in the solution, the concentration of phosphorus-containing organic material in the solution, or the concentration of hydroxyl units on the metal oxide particles. As a precautionary measure, the coated particles may be treated in a solvent which will remove the physically adsorbed molecules.
It should be noted in this regard that when hydrophobic or oleophilic surfaces are desired, it is the long chain hydrocarbon R groups, not the short chain R' groups, which principally interact with the respective organic materials being passed though the column to provide the independent peaks identifying the particular organic material passing through the column at various rates of elution. The principal function of the shorter chain R' groups is to react with any remaining hydroxyl groups on the aluminum oxide/hydroxide support material so that the non-polar group or groups of the organic material passing through the column will interact with the non-polar packing material--rather than the polarized end of the organic molecule passing through the column interacting with exposed hydroxyl groups on the support material--so that a true reversed phase profile through the chromatographic column is maintained. Thus, the shorter chain phosphorus-containing organic molecule must be reacted with the support surface in an amount sufficient to bond to substantially all reactive hydroxyl sites remaining on the support surface after the initial treatment with the one or more longer chain phosphorus-containing molecules.
After formation of the packing material, the material may be treated in either a basic or acidic solution, or both, to remove any weakly adsorbed molecules on the particles. This ensures that all of the molecules remaining are bonded to the hydroxyl groups on the metal oxide/hydroxide surface and not to one another, thus assuring formation of the desired monomolecular layer stable over a wide range of pH.
In a preferred embodiment, a sodium hydroxide solution, having a concentration ranging from about 0.001 to 1 molar and buffered with sufficient sodium bicarbonate to maintain the pH in a range of from about 9-12, may be used as the wash solution to remove the excess organic acid molecules, leaving only the desired bonded monomolecular layer. Other wash solutions which may be used instead of the sodium hydroxide include potassium hydroxide and ammonium hydroxide solutions which may also be buffered to provide approximately the same pH range.
For example, the wash solution may also comprise a weak acid such as a carboxylic acid, e.g., acetic or formic acid or a weak mineral acid (0.1-2N) such as sulfuric, nitric, or hydrochloric acid. The wash solution might also comprise an alcohol such as isopropanol or butanol. However, the use of bases as wash solutions are preferred since the resulting salts, e.g., sodium or potassium salts, are more soluble.
The resulting chromatographic packing material is stable at pH ranges of from 1-14 and has good stability in the range of 1-12 while still maintaining high efficiency of separation with N numbers of 18,000 to as high as over 35,000, where N equals the theoretical plates which equals 5.53 times (retention time of peak/width of peak at half of its height)2.
The following examples will serve to better illustrate the invention.
To prepare the aluminum hydroxide crystals described and claimed in the aforementioned Wilhelmy patent application, an aluminate solution was prepared using reagent grade sodium hydroxide pellets, 99.96% pure aluminum powder (Alcoa 7123 atomized powder) and freshly boiled distilled water. About 260 grams/liter of sodium hydroxide pellets were added to a Teflon bottle twice the volume of the final solution. To this was slowly added water with stirring until the solution was approximately one-half the final volume (1/2 liters). The bottle was then immersed in cold water. 123 grams of the aluminum powder was then slowly added to the solution as a slurry. After the addition was completed, the suspension was placed in an oil bath and heated to boiling. The contents were boiled until the solution was clear. This resulting solution was cooled to room temperature and diluted to a volume of 1 liter. The solution was allowed to stand overnight and filtered the following day using a 0.45 micrometer Metricel DM membrane (Gelman Instrument Co.).
The resulting solution having a [Al3+ ]:[NaOH] ratio of 0.7 was divided into two portions. One portion was diluted with an NaOH solution to form a final solution having a [Al3+ ]:[NaOH]ratio of 0.6. The two solutions were aged at 75° C. for 3 and 9 hours, respectively. Aluminum hydroxide was then precipitated from each of the samples and the diameter to length ratio was determined as shown in the following table:
TABLE I______________________________________Sample Molarity Al.sup.3+ :NaOH Diameter/LengthNumber of NaOH Ratio of Crystals______________________________________1 0.75 0.6 0.32 1.50 0.6 0.53 3.00 0.6 2.04 4.50 0.6 1.65 6.00 0.6 11.06 0.75 0.7 0.37 1.50 0.7 0.78 3.00 0.7 1.29 4.50 0.7 1.9______________________________________
The results indicate that for both 0.6 and 0.7 ratios, the crystals increase in their diameteR'length ratios as the concentration of the sodium hydroxide increases, i.e., the crystals become more lamellar.
To further demonstrate the invention, lamellar alumina particles, made in accordance with the procedures of Example 1, and having a median particle size of 12.5 microns were calcined by heating to 300° C. at 5° C. per minute and then held at that temperature for 2 hours to allow slow dehydroxylation of the aluminum hydroxide. The alumina was then heated to 500° C. to decompose any remaining aluminum hydroxide. The calcined alumina was then slurried in deionized water and treated with nitric acid until the pH reached about 6.5. This calcination and neutralization procedure was repeated until a pH below 7 was obtained indicating sufficient sodium removal from the particles.
80 grams of the particles were then treated with varying amounts of octadecyl phosphonic acid, (C18) as listed in Table II, until the surface concentration of the octadecyl phosphonic acid on the alumina surface reached between 4.39 to 4.94 micromoles/square meter. The reaction was carried out at about the boiling point of the n-butanol solvent, i.e., about 110°-120° C. for 60 minutes while stirring the mixture at 200 rpm.
Some of the treated alumina was then capped by treating with methyl phosphonic acid until a concentration of about 1.40 micromoles of methyl phosphonic acid per m2 of alumina was bonded to the alumina, i.e., the remaining alumina surfaces not reacted with the octadecyl phosphonic acid were reacted with a lower molecular weight phosphonic acid. Other material was capped by treating with phenyl phosphonic acid until a concentration of about 0.87 to about 0.93 micromoles/m2 alumina was reached. Some of the octadecyl phosphonic acid treated alumina was not further reacted or "capped".
The treated alumina, in each case, was slurried in 2-propanol (1 ml/gm of alumina) and a sodium bicarbonate/sodium hydroxide pH 10 buffer was added. Each sample was then shaken for 4 hours, allowed to settle, and the supernatant was decanted. This procedure was then repeated using a 5 ml/gm ratio of 2-propanol/alumina. Finally, the product was slurried in methol at 5 ml/gm, decanted and allowed to vacuum dry overnight at 60° C. followed by 1 hour under vacuum at 125° C.
TABLE II______________________________________Octadecyl Phosphonic Acid Supplied and Bound to Alumina Alumina Surface Fed ReactedSample Area Micromoles of Micromoles ofNo. m.sup.2 /g C-18/m.sup.2 Al.sub.2 O.sub.3 C-18/m.sup.2 Al.sub.2 O.sub.3______________________________________1 88.2 6.33 4.532 86.4 5.75 4.393 88.2 6.33 4.734 86.4 5.75 4.575 88.2 7.45 4.536 86.4 6.49 4.577 88.2 7.45 4.948 86.4 6.49 4.61______________________________________
Chromatographic columns of 0.46 cm I.D. and 25 cm length were then packed respectively with about 4 grams of alumina reacted only with octadecyl phosphonic acid (uncapped), reacted with octadecyl phosphonic acid and then capped with methyl phosphonic acid, or reacted with octadecyl phosphonic acid and then caploed with phenyl phosphonic acid.
Test solutions were then prepared containing 90 mg of theophylline, 90 mg of p-nitroaniline, 200 microliters of methyl benzoate, 600 microliters of phenetole, and 1800 microliters of o-xylene dissolved in a solvent mixture of 30 vol. % acetonitrile, 30 vol. % methanol and 40 vol. % water (prior to mixing) to demonstrate the efficiency of the separations at various pH levels.
These test solutions was then injected into each packed column in 10 microliter aliquots at a flow rate of 1.0 ml/minute at room temperature. Five peaks were detected by a variable wavelength spectrometer corresponding to the five components of the test solution. The elution order of the components of the test solution in each case was theophylline, p-nitroaniline, methyl benzoate, phenetole, and o-xylene. For purposes of this invention it is only important to note the elution times of the fifth peak in each case.
The results are shown in Table V below. The variation in fifth peak elution times for capped and uncapped octadecyl phosphonic acid groups is shown in Table VI. Higher surface concentration of organic groups on the packing in a liquid chromatography column increases the elution time of non-polar components in mixtures being separated. Fifth peak elution times for uncapped treated alumina are compared to the elution times for treated alumina and also capped with methyl phosphonic acid. The columns with the longest elution times are those packed with methyl phosphonic acid capped packings.
TABLE V______________________________________ Fifth PeakColumn Capping ElutionNo. Reagent Time/min. Comments______________________________________500 Methyl 11.16 Theoretical plates calculated501 Methyl 11.20 by integrator502 Methyl 11.45 Theoretical plates calculated503 Methyl 11.39 by integrator537 -- 10.37 Stable568 -- 9.15 Stable, CHC1PV3PV in pack liquid523 Phenyl 11.06 Unstable base line553 -- 10.47 Stable base line515 Phenyl 11.21 Unstable base line557 -- 10.02 Stable base line512 Methyl 10.22 Leading edge asymmetry513 Methyl 10.02 Leading edge asymmetry540 -- 8.82 Good symmetry541 -- 10.54 Good symmetry542 -- 9.24 Good symmetry543 -- 10.08 Leading edge symmetry544 -- 9.78550 -- 9.64516 Phenyl 11.57 Unstable base line555 -- 10.75 Stable base line508 Methyl 10.34 Some Peak asymetry, leading edge538 -- 9.75 Good peak shape566 -- 8.94 Good peak shape, but wide567 Methyl 9.64 Chloroform solvent packing509 Methyl 9.88 Leading edge asymmetry511 Methyl 10.64 Leading edge asymmetry539 -- 9.11 Leading edge asymmetry504 Phenyl 11.04 Unstable base line505 Phenyl 11.27 Unstable base line506 -- 9.32 Stable base line507 -- 8.81 Stable base line 8.94 Stable base line523 Phenyl 11.055 Bled bonded phase514 Phenyl 11.54 Bleeding, unstable base line565 -- 10.22 Stable base line______________________________________
TABLE VI______________________________________With Methyl Phosphonic Without Methyl PhosphonicAcid Cap Acid Cap Fifth Peak Fifth PeakColumn Retention Column RetentionNo. Time/min. No. Time/min.______________________________________500 11.16 537 10.37501 11.20 568 9.15502 11.45503 11.39512 10.22 540 8.82513 10.02 541 10.54 542 9.24 543 10.08 544 9.78 550 9.64508 10.43 538 9.75567 9.64 566 8.94509 9.88 539 9.11511 10.64______________________________________
Uisng the same columns as in Example 2, the same solution was run through the columns, but at various pHs to show the stability of the absorbent material fo the invention over a wide pH range. The results are shown in the chromatograms of FIG. 9a-9e. In FIG. 9a, the mobile phase was a 50 wt. % acetonitrile/ 50 wt. % water mixture having a pH, measured before addition of the organic phase, of 7. In FIG. 9b, the mobile phase was a 50 wt. % acetonitrile/ 50 wt. % water mixture with 0.05 wt. % Tris (2-amino-2-hydroxy methyl-1,3-propane diol) added to raise the pH to 9. In FIG. 9c, the mobile phase was a 50 wt. % acetonitrile/ 50 wt. % water mixture with sufficient sodium bicarbonate/sodium hydroxide added to raise the pH to 10. In FIG. 9d, the mobile phase was a 50 wt. % acetonitrile/ 50 wt. % water mixture with sufficient 0.1 M sulfuric acid added to lower the pH to 1. In FIG. 9e, the mobile phase was a 50 wt. % acetonitrile/ 50 wt. % water mixture with sufficient trifluoroacetic acid added to lower the pH to 2. The elution rate was about 0.7 ml/minute with absorbents monitored at 254 nanometers measured using a variable wavelength (uv/vis) spectrometer with 2.56 absorbence units at full scale sensitivity.
Using the same type of separation columns as in Example 2 above, amine mixtures of aniline, N-methyl aniline, and N,N-dimethyl aniline were eluted with solvents ranging in pH from 7-11. The results are shown in the chromatograms of FIGS. 10a-10c. The mobile phase in FIG. 10a was a 50 wt. % acetonitrile/ 50 wt. % water mixture having a pH of 7. The mobile phase in FIG. 10b was a 50 wt. % acetonitrile/ 50 wt. % water mixture with sufficient 0.05M Tris added to raise the pH to 9. The mobile phase in FIG. 10c was a 50 wt. % acetonitrile/ 50 wt. % water mixture with sufficient sodium bicarbonate/sodium hydroxide added to raise the pH to 10. The elution rate was again about 0.7 ml/minute with the 254 nanometer wavelength measured using a variable wavelength (uv/vis) spectrometer with 2.56 absorbent units at full scale sensitivity.
The peaks show surprisingly good symmetry and are not skewed. Amine compounds separated on reverse phase silica-packed columns usually show assymetric peaks.
To demonstrate the separation of 5 amino acid peptides using the material of the invention, a solution was made up comprising 5.5 ppm methionine enkephalin and 5.1 ppm leucine enkephalin dissolved in a solvent comprising 25% acetonitrile, 75% water and 0.1% trifluoroacetic acid and having a pH of 1.5. the flow rate in this case was 2 ml/minute with the detector wavelength set at 210 nanometers. The results are shown in FIG. 11 which indicates both the baseline separation and excellent peak symmetry possible using the material of the invention.
Thus the invention provides an improved chromatographic packing material with an extended area which exhibits good stability over a wide pH range with good separation efficiency.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3013904 *||Apr 13, 1959||Dec 19, 1961||Du Pont||Substrate having an organic polymer containing pentavalent phosphorus bonded thereto|
|US4202798 *||Oct 30, 1978||May 13, 1980||Atlantic Richfield Company||Phosphorous-containing catalyst and method for preparing and using same|
|US4308079 *||Jun 16, 1980||Dec 29, 1981||Martin Marietta Corporation||Durability of adhesively bonded aluminum structures and method for inhibiting the conversion of aluminum oxide to aluminum hydroxide|
|US4382016 *||Jun 23, 1982||May 3, 1983||American Cyanamid Company||Extractant for the selective removal of cobalt(II) from aqueous solutions|
|US4506628 *||Jul 13, 1983||Mar 26, 1985||Stockel Richard F||Animal litter|
|US4786628 *||Mar 9, 1987||Nov 22, 1988||Aluminum Company Of America||Chromatographic packings comprising metal oxide/hydroxide reacted with phosphonic acid|
|US4788176 *||Mar 9, 1987||Nov 29, 1988||Aluminum Company Of America||Adsorbent comprising metal oxide/hydroxide particles reacted with one or more phosphorous-containing materials having selected organic radicals attached thereto|
|US4816159 *||Aug 31, 1987||Mar 28, 1989||Aluminum Company Of America||Supercritical fluid chromatography packing material|
|US4822593 *||Mar 6, 1987||Apr 18, 1989||Aluminum Company Of America||Control of form of crystal precipitation of aluminum hydroxide using cosolvents and varying caustic concentration|
|US4871711 *||Mar 9, 1987||Oct 3, 1989||Aluminum Company Of America||Active material produced from metal oxide/hydroxide particles and phosphate esters|
|US4900537 *||Dec 11, 1986||Feb 13, 1990||Biotage, Inc.||Control of form of crystal precipitation of aluminum hydroxide using cosolvents and varying caustic concentration|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5190658 *||Feb 3, 1992||Mar 2, 1993||Monsanto Company||Method for size exclusion chromatography|
|US5595709 *||May 3, 1994||Jan 21, 1997||Chromatofast||Instrument for measuring non-methane organic gases in gas samples|
|US5611927 *||Mar 7, 1996||Mar 18, 1997||Waterlink, Inc.||System for removing nutrients from wastewater|
|US5656566 *||Apr 6, 1995||Aug 12, 1997||Imperial Chemical Industries Plc||Catalysts|
|US5882736 *||Aug 20, 1997||Mar 16, 1999||Atotech Deutschland Gmbh||palladium layers deposition process|
|US6160190 *||Jun 3, 1999||Dec 12, 2000||E. I. Du Pont De Nemours And Company||Alkylation of aromatic compounds using a sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide|
|US6241891 *||Sep 20, 1999||Jun 5, 2001||Nomura Chemical Co., Ltd.||Method of using stationary phase in reversed phase chromatography, and reversed phase chromatograph apparatus comprising stationary phase|
|US6958307 *||Aug 16, 2001||Oct 25, 2005||Institut Francais Du Petrole||Materials comprising organic phosphorous-containing groups bonded to a mineral oxide via oxygen atoms|
|US7125492||Jul 17, 2003||Oct 24, 2006||Agilent Technologies, Inc.||Additives for reversed-phase HPLC mobile phases|
|US7964380 *||Jan 23, 2006||Jun 21, 2011||Argylia Technologies||Nanoparticles for manipulation of biopolymers and methods of thereof|
|US20020023573 *||Aug 16, 2001||Feb 28, 2002||Institut Francais Du Petrole||Materials comprising organic phosphorous-containing groups bonded to a mineral oxide via oxygen atoms|
|US20040217061 *||Feb 5, 2004||Nov 4, 2004||The Procter & Gamble Company||Doped adsorbent materials with enhanced activity|
|US20050011836 *||Jul 17, 2003||Jan 20, 2005||Brian Bidlingmeyer||Additives for reversed-phase HPLC mobile phases|
|US20060177855 *||Jan 23, 2006||Aug 10, 2006||Utermohlen Joseph G||Nanoparticles for manipulation of biopolymers and methods of thereof|
|US20070281854 *||Nov 5, 2004||Dec 6, 2007||Commonwealth Scientific And Industrial Research Organisation||Metal Oxide/Hydroxide Materials|
|US20090101581 *||Apr 25, 2008||Apr 23, 2009||Hanfa Zou||Immobilized titanium ion affinity chromatography material and its preparation and application|
|WO1993015400A1 *||Jan 27, 1993||Aug 5, 1993||Monsanto Company||Apparatus and method for size exclusion chromatography|
|U.S. Classification||502/401, 210/198.2, 502/407, 210/635, 502/415, 427/220, 502/403, 502/404, 95/88, 502/402, 210/656|
|Cooperative Classification||B01J20/286, B82Y40/00, B01J20/3248, B82Y30/00, B01J20/287|
|European Classification||B82Y30/00, B01J20/287, B01J20/286, B01J20/32F8B4F, B82Y40/00|
|Dec 1, 1988||AS||Assignment|
Owner name: ALUMINUM COMPANY, PITTSBURGH, PA A CORP. OF PA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WIESERMAN, LARRY F.;WEFERS, KARL;CROSS, KATHRYN;AND OTHERS;REEL/FRAME:004969/0056;SIGNING DATES FROM 19881117 TO 19881122
Owner name: ALUMINUM COMPANY OF AMERICA, PITTSBURGH, PA A CORP
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WIESERMAN, LARRY F.;WEFERS, KARL;CROSS, KATHRYN;AND OTHERS;REEL/FRAME:004969/0056;SIGNING DATES FROM 19881117 TO 19881122
Owner name: ALUMINUM COMPANY, PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WIESERMAN, LARRY F.;WEFERS, KARL;CROSS, KATHRYN;AND OTHERS;SIGNING DATES FROM 19881117 TO 19881122;REEL/FRAME:004969/0056
Owner name: ALUMINUM COMPANY OF AMERICA, PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WIESERMAN, LARRY F.;WEFERS, KARL;CROSS, KATHRYN;AND OTHERS;SIGNING DATES FROM 19881117 TO 19881122;REEL/FRAME:004969/0056
|Aug 11, 1989||AS||Assignment|
Owner name: BIOTAGE, INC., MASSACHUSETTS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ALUMINUM COMPANY OF AMERICA;REEL/FRAME:005137/0401
Effective date: 19890526
|Nov 27, 1989||AS||Assignment|
Owner name: BIOTAGE, INC., MASSACHUSETTS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ALUMINUM COMPANY OF AMERICA;REEL/FRAME:005184/0708
Effective date: 19891122
|Nov 8, 1990||AS||Assignment|
Owner name: ALUMINUM COMPANY OF AMERICA, PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BIOTAGE, INC.;REEL/FRAME:005505/0957
Effective date: 19901016
|Jun 29, 1993||CC||Certificate of correction|
|Mar 14, 1995||REMI||Maintenance fee reminder mailed|
|Aug 6, 1995||LAPS||Lapse for failure to pay maintenance fees|
|Aug 7, 1995||FPAY||Fee payment|
Year of fee payment: 4
|Aug 7, 1995||SULP||Surcharge for late payment|
|Oct 17, 1995||FP||Expired due to failure to pay maintenance fee|
Effective date: 19950809


text:
NYS Entity Status
NYS Filing Date
JULY 01, 2014
NYS DOS ID#
NYS Entity Type
DOMESTIC BUSINESS CORPORATION
2014 - DADDY'S PIZZA & PASTA CORP
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Diffusion Under Thermal Equilibrium
- Pp. 3-34 (32)Kunihiro Suzuki
We derive a diffusion flux and diffusion equation step by step, starting with a rough sketch one to a practical one. The flux is described with the paring with point defects, and the dependence of diffusion coefficients on doping concentration is emerged. We can predict diffusion profiles by solving the equation.


text:
Regulators allow Charter to move ahead with takeover of Time Warner CableApril 25, 2016
Federal regulators are allowing Charter Communications to move ahead with its $78.7 billion takeover of Time Warner Cable, a massive deal that would create the second-largest cable and Internet provider in the country.
The move also means Charter can purchase Bright House Networks for $10.4 billion. The combined company would instantly become a powerhouse in the telecommunications industry with about 24 million customers in regions such as New York, Dallas, central Florida, Detroit, and Los Angeles.
Washington plans to put several conditions on the merger that will last for seven years and aim to enhance competition in online video and broadband service. For instance, the combined company would be prevented from fashioning agreements with companies like Netflix and other streaming services that force them to pay a fee to reach consumers' devices. The merged firm also would be prohibited from imposing data caps on home internet service which could discourage watching videos online.
"The conditions that will be imposed ensure Charter's current consumer-friendly and pro-broadband businesses practices will be maintained by New Charter," Charter said in a statement.
Federal Communications Commission chairman Tom Wheeler said Monday that the conditions would "directly benefit consumers by bringing and protecting competition to the video marketplace and increasing broadband deployment." The matter must still win a vote by the agency's five commissioners, who are expected to approve the deal.
To read this article in one of Houston's most-spoken languages, click on the button below.
The Justice Department, which also approved the deal, valued the acquisition of Time Warner Cable and Bright House Networks at about $88 billion.
Charter's stock was up nearly 5 percent Monday afternoon; Time Warner Cable's was up 3.8 percent.

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The World Wealth report states that high net worth individuals put 31.6 percent of their money on luxury watches, gems, and jewelry. Gems and jewelry seem to be more likely choices because they can be bartered and rise in value, but watches—that’s interesting.
This makes watches one of the top passion investments, even surpassing fine art, cars, and toys. According to the report, the value of watches keeps on rising in the past years regardless of economic instability—making it a good hedge against inflation, for example.
Watch expert Steve Kivel owns and runs Watch Central, a go-to hub for restoring valuable timepieces. Kivel says well-thought-of watch portfolios should include models from top brands, and each piece should at least have a 30 to 50 percent value increase over a period of 10 years.
Rolex still on top
Rolex remains to be the most sought-after investment grade timepiece all over the world.
Last month, a Rolex sale at Christie’s in Geneva raised a sum of $13.2 million. The watch was one of the 50 Rolex Oyster Daytonas made 50 years ago that was worth more than $1 million. Another example of a Rolex timepiece appreciating over time is the Rolex 1019 Milgauss. The model retailed for $300 in the ‘60s and is now worth $25,000.
The Rolex Submariner, which Kivel refers to as “the Apple stock of watches,” meanwhile, whose current value is at $7,500, is expected to shoot up to 50 percent in 10 years. “You can sleep at night knowing that this could be one of the things locked up in your vault that is going to grow in value,” says Kivel to Bloomberg.
What other watch brands and models are worth investing in?
The Breitling Navitimer’s $5,395 current value is expected to shoot up to 30 percent in 10 years. There are only 2,000 pieces of the limited edition Navitimer Montbrilliant Legend, and investors seeking for a modern watch that can potentially to soar in value over time should consider this piece a must-have.
The Omega Cosmic Moon Phase can be bought at $5,500 today, and experts believe that its 10-year projection increase can go up as high as 50-55 percent.
A Tudor Heritage Black Bay piece is worth $3,554 today and collectors are won over by the modern design of the leather and fabric straps and the detail work all over the piece.
Vintage watches fetch more value
An investment-grade watch doesn’t necessarily mean that it should have state-of-the-art features. In some cases, simplicity reigns over extravagance. Patek Philippe is an epitome of this. The most expensive traditional wristwatch sold back in 2010 was a 1944 Patek Philippe piece that was bought for $5.6 million in 2010. Out of the 100 most expensive watches that were auctioned in history, 80 watches belonged to the brand.
Dan Wade of Paul Fraser Collectibles said that Patek Phillippe watches command high prices because of its workmanship, high-quality materials, and limited production. “The prestige of the Patek Philippe name makes its timepieces highly sought after; their scarcity pushes prices up,” said Wade.
Vintage watches such as the Patek Philippe are more likely to be assigned higher auction prices than brand new models. Toby Sutton of Watches of Knightsbridge, a specialist auction house for timepieces, believes that investors can get better value if they choose to put their money on antique pieces. “I would say 99 times out of 100 it is better value buying a pre-owned or vintage watch over brand new. Many pre-owned or vintage watches have increased considerably in value over the past decade,” said Sutton.
The value of Patek Philippe pieces is known to withstand tough economic setbacks. A recession wouldn’t affect the expected 50 percent value increase within a 10-year period of a Patek Philippe Calatrava that costs $9,750 today.
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Anthony Joshua sends message to Dillian Whyte after upset to Alexander Povetkin
Written by on August 23, 2020
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Anthony Joshua says Dillian Whyte’s shock KO defeat by Alexander Povetkin was only a ‘blip’ in his career and believes he will come back stronger.
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Crisis Group’s Senior Consultant for Southern Africa, Piers Pigou has bemoaned the erosion of the majority of Zimbabweans’ purchasing power as the value of the “Funny Money”, the RTGS dollars. Writing on social media on Wednesday, Pigou said:
If you have USD, and only a select do, prices of goods and services are in fact very reasonable; BUT the majority are reliant on this “funny money”, the RTGS $ whose value continues to erode and every day most Zimbabweans see their cost of living climb. Is there an end in sight?
Pigou was commenting on an earlier tweet by journalist and political commentator Hopewell Chin’ono who had said:
To fully understand what is happening to Mthuli Ncube’s economy daily, you should look at the price of goods and the exchange rate.
Bread is now at RTGS$7, that means a teacher’s salary is now worth 49 loaves of bread or 15 bottles of Mazoe. Tomorrow it will be worth fewer loaves!


text:
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I had a vague idea of how this play was going to go having growing up watching Bugs Bunny’s 3rd Movie: 1001 Rabbit Tales on VHS repetitively and having a picture book … Continue reading Arabian Nights @ Hoxton Hall (21/09/2018)
Only thing I knew was The Old Vic had a history of having outstanding production with the occasion distinguished actors such as Ian McKellen. This would mark the first ever time … Continue reading A Monster Calls @ Old Vic Theatre (03/07/2018)
I granted myself another writing break due having a regular minor emotional breakdown midweek. I’m back with a review with two nights being sleep deprived. It was my parent’s 35th … Continue reading [Review] Iris Theatre Presents: Hansel & Gretel
A mystical stage adaptation of a certain young witch’s adventure to an unfamiliar city.

domain: literature


A multibillion-dollar project to connect the Long Island Rail Road to Grand Central Terminal may have a nice side effect for people in New York City’s northern suburbs.
It might also make it possible for Metro-North trains to run directly into Penn Station.
The New York Post reports that the Metropolitan Transportation Authority thinks its $7 billion project to allow LIRR trains to Grand Central will free up a lot of track space at Penn Station — maybe even enough so that Metro-North trains will finally be able to stop there too.
The newspaper says the MTA is now studying whether it could bring in Metro-North trains on existing tracks, and possibly
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In December/January, the United Kingdom imported a third of its fresh fruit and vegetables from Spain. With seven percent, the Netherlands supplied the second most produce in those months. When you include re-exports, that rises to ten percent.
Last December, those imports amounted to 150.000 tons from Spain and 170.000 tons in January. In those two months, the Netherlands sent 33.000 and 38.000 tons of goods, respectively, to the UK. When you include re-exports, the Netherlands exported 50.000 tons of fresh produce in each of those months to that country.
That's an average of 12.000 tons - 480 trucks carrying 25 tons each - per week. In December and January, an average of 100 trucks transported fresh vegetables from/via the Netherlands to the United Kingdom per (working) day. These goods also come from many countries. And most of them transport these products by sea.
More than half of most products come from overseas
Over the year as a whole, the UK depends on fresh vegetable imports half the time. For example, the UK grows 70.000 tons of tomatoes but imports 390.000 tonnes. The situation is different for products such as cauliflower and broccoli. But even with local production of 150.000 tons, the United Kingdom still imports 120.000 tons of these products annually. The UK also imports a lot of onions, lettuce, cucumbers, and bell peppers.
That country's production of vegetables continues to decline too. The cultivation of fresh vegetables in the United Kingdom is also quite one-sided. Carrots, of which 850.000 tons are grown, account for a third of total vegetable production. Then, in second place, they grow between 350.000 to 400.000 tons of onions. There is a modest protected crop, amounting to 250.000 to 300.000 tons. When it comes to fresh fruit, the UK relies on imports almost 85% of the time. They are, however, growing more apples and strawberries.

domain: agronomy


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Jabalpur To Manmad Trains
Following is the list of all the trains running between Jabalpur to ManmadRailwayStations:
More About - Jabalpur To Manmad Trains
There are a number of trains you can choose from if you are travelling from Jabalpur to Manmad. Here are some trains that run from Jabalpur to Manmad are Dikshabhumi Exp, Saket Express, Bsb Ltt Sup Exp, Guwahati Mumbai Lokmanyatilak T Express, Cstm Garibrath, Dbg Pune Exp, Rajendranagar Lokmanyatilak T Express, Bgp Ltt Express, Ranchi Lokmanyatilak T Express, Asn Cstm Expres and etc. You can board your train from different stations such as Jabalpur. There are different trains that travel and time taken by these trains varies from29 hrs 55 mins to 10 hours 40 mins. Choose your train according to your suitability from trains that run on daily basis like Rajendranagar Lokmanyatilak T Express, Pnbe Pune Exp, Mahanagari Exp, Gorakhpur lokmanyatilak t Express, Rjpb Cstm Exp, Hwh Mumbai Mail and trains that run sporadically like Gkp Pune Expres, Bsb Cstm Spl, Mau Ltt Spl, Hwh Ltt Special, Bgp Ltt Express, Bsb Ltt Sup Exp, Gyan Ganga Exp, Pnbe Vsg Expres, Rae Bareli Saket Link Express, Saket Express etc. There are different trains passing from various stations from Mumbai. The stations include Jabalpur( like Bsb Cstm Spl, Mfp Ltt Specia, Asn Cstm Expres, Mau Ltt Spl, Gkp Pune Expres, Gkp Pune Spl, Guwahati Lokmanyatilak T Express, Bsb Ltt Sup Exp, Gyan Ganga Superfast, Ranchi Lokmanyatilak T Express ).

domain: geography


The most used and abused plumbing fixture in homes today is the toilet. A good quality toilet can last almost forever if your water isn’t corrosive and you properly maintain its inner workings. A running toilet can produce a high water bill and is worth the money in repairs, which could be less than the overage on your next statement.
Inside the Tank
If your toilet is running after you flush, try jiggling the handle. If there is some play to it before it gives resistance, you will need to look in the tank by removing the lid. Jiggling the handle can solve the running problem temporarily. There are components inside that regulate the emptying and filling of water to ensure there is pressure for the next flush. The most common problems are a faulty flapper or float that gets stuck and partially submerged under water.
This is the large valve on the bottom of the tank. It has a chain attached to it. When the handle is flushed, the plastic arm lifts the flapper by the attached chain. This allows the water to drain. When the handle is released, the slack in the chain allows the flapper to float back down. If it has begun to rot, it will not seal properly and the water will continue to drain. If you suspect the flapper, you can run your finger along the bottom side and if there is a black residue, it is time to replace the valve.
These flapper replacement kits include a new chain, seal and silicone sealant. They are everywhere at your home improvement stores and online. They typically cost around $10-$20 depending on your toilet.
When you look inside the tank you will notice a float, also known as the toilet ball, but not always the shape of a ball. If it is not resting on top of the water, it will need to be replaced. It is possible the float is set too high. This causes the water level to be set too high and will continuously run as the overflow tube will prevent the water from ever reaching the float. A simple clockwise turn or two of the screw that attaches it to the fill valve will bring it back down.
It is the least common of the three reasons for a toilet to run continuously, but the fill valve may go bad. It is also a simple and inexpensive way to prevent costly water bills.


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Books by Brights
Less Than Human: Solving the Puzzle of Dehumanization
Less Than Human is a book about our pervasive tendency to conceive of other human beings as subhuman creatures - as vermin, parasites, predators or prey - and the role that this plays in genocide, war, slavery and other forms of atrocity. Drawing on an interdisciplinary mix of history, anthropology, psychology, primatology and philosophy, Less Than Human traces the history of the concept of dehumanization from ancient Greece to the present, and gives an analysis of what exactly is going on when we regard our fellow human beings as less than human. It will be published in March 2011 by St. Martin's Press, and is available for pre-order from Amazon.
About the Author
Dr. David Livingstone Smith is professor of philosophy and cofounder and director of the Institute for Cognitive Science and Evolutionary Psychology at the University of New England. He and his wife live in Portland, Maine.

domain: library


In a 5 to 3 vote, Macon-Bibb commissioners approved transferring garbage services to a private company, raising residents garbage fees to $20 per month.
The approved solid waste department’s plan puts private company Advanced Disposal in charge of handling all garbage collection throughout Macon-Bibb.
This switch leaves current solid waste employees to focus only on recycling, collecting yard waste materials, and reporting illegal dumping.
Former city residents will face a $5 increase per month, and those in the former unincorporated area will see a $7.25 increase.
Even though both Solid Waste Department Director Kevin Barkley and Mayor Robert Reichert promise that current solid waste employees will not lose their jobs, Commissioner Bert Bivins says a promise isn’t enough.
Commissioner Bivins says, “Why is it that we can’t just reverse the roles and let our people pick up the garbage and let the other people do all the other stuff? I think that there’s been a decision made by somebody in the past that we’re going to give all of this work to the contractors, and I think that’s what we’re upholding.”
Bivins presented a motion to switch the roles during commission, but it failed after only having the support of Commissioner Elaine Lucas.


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6 Braces Treatment Mistakes to Avoid When Getting Teeth Straightened
Posted on October 2, 2020
Successful orthodontic treatment can be life-changing. In addition to the straight teeth you will obtain, braces can give you a better smile, facial structure, and oral health. However, the road to treating malocclusions does have some guidelines to follow, which may derail your treatment plan if you do not follow them. In order for you to get that perfect set of teeth, you will need to avoid these six mistakes that are common during orthodontic treatment.
1. Not Getting Braces from an Orthodontist
While it may sound convenient at first, starting orthodontic treatment with a dental provider who is not a certified orthodontist may not be a wise decision in the long run. General dentists receive less education than orthodontists on the proper practices to achieve straight teeth. Orthodontists must attend a two-year residency program on top of their four years in dental school. Some orthodontists are also board-certified, which means they have completed even more hours of training after their orthodontic residency. Needless to say, orthodontists will have the right skills and expertise to advise on the best treatment option for your misaligned teeth.
2. Thinking Braces are Only for Children
Braces treatments are ideal for all age groups. The American Association for Orthodontists estimates there are over 4 million Americans wearing braces today. However, the board also recommends early orthodontic treatment suggesting the first orthodontic treatment at the age of seven. At this age, your orthodontist can inspect the teeth confidently for any misalignment or bad bites. However, even if you are already past your teenage years it is not too late to straighten your teeth. In fact, 25% of Americans wearing braces are adults.
3. Forgetting to Practice Proper Oral Hygiene
Orthodontic braces demand a higher level of dental care and hygiene throughout the treatment process. Food particles may stick in between the brackets and teeth, leading to plaque and tartar buildup.
Poor oral health care can also lead to teeth discoloration, halitosis, or worse gum disease. Always adhere to strict dental hygiene by brushing with a soft interdental toothbrush after every meal. Remember to floss at least once every day.
4. Eating “Forbidden” Foods
Your orthodontist will probably give you a list of foods that you need to avoid during the treatment period. Hard and sticky foods require more biting force while chewing and may get stuck in your brackets. It is important to follow the food guidelines provided by your doctor.
You can also opt for Invisalign aligners. These allow you to remove them while eating your favorite meals and place them back when you finish.
5. Skipping Orthodontic Appointments
You will have to make regular trips to the orthodontist office for your follow-up appointments. These check-ups allow the orthodontists to monitor your progress and adjust the braces accordingly. You also get the opportunity to ask any questions about your treatment plan and if needed replace any broken parts.
6. Restricting Yourself to Metal Braces
Traditional metal brackets and wires are effective but require a certain level of care. It is important to keep a higher standard of oral hygiene during this time. However, advances in technology within the orthodontic sphere have led to the development of other alternatives such as Invisalign. The aligners are more subtle and comfortable while being just as efficient as metal braces. It may be a worthwhile option to consider if you are concerned about the maintenance associated with braces.
Braces and aligners can help you attain straight teeth. Avoiding the six mistakes above to fasten your teeth realignment process and avoid any issues during treatment. For more information on braces, feel free to consult Parker Orthodontics.

domain: medical


A suppressed, single-shot, break-barrel air rifle ideal for hunting small to medium game, the ASP20 (starting at $349) makes its debut as the first SIG Sauer airgun built in the U.S.A. Available in either .177 or .22 cal. with the option of a wood or synthetic stock, it features a two-stage adjustable trigger with eight different pull weights between 2 lbs., 8 ozs., and 4 lbs. The ASP20 requires only 33-35 lbs. of force to cock, measures 45.6” long and weighs 8 lbs., 8 ozs. Picatinny rail atop the air rifle allows for the mounting of a scope. For more on this air rifle, please visit sigsauer.com.
Product Preview: SIG Sauer ASP20 Air Rifle
Making Modern Colt Revolvers
Colt re-entered the modern double-action revolver market in a big way, bringing back legacy designs like the Cobra, Python and Anaconda. These guns aren't made the old way, though. They're produced using the latest in cutting-edge manufacturing technology.
New For 2023: EAA Girsan MC 14T
European American Armory Corp now imports Girsan's MC 14T, a compact, .380 ACP-chambered handgun that can be easily loaded and unloaded, thanks to its tip-up barrel design.
Updating An M1 Carbine
Many M1 carbine owners would never consider such modifications to a wartime gun with significant provenance, those who have run-of-the-mill arsenal-rebuilt or commercial examples, and who are willing to experiment, are likely to find that the M1 carbine can provide service comparable to modern PDW-type platforms.
Editor’s Choice: BamBeds For Toyota Tacoma Trucks
Designed by a mechanical engineer, BamBeds is a multi-purpose sleeping and gear storage system for '05-present Toyota Tacoma short- and long-bed pickup trucks that lends the popular platform even greater utility for the hunter or camper.
In Memoriam: John Linebaugh—1955-2023
John Linebaugh, inventor of the .500 and .475 Linebaugh cartridges and custom pistolsmith, died March 19 at his home in Clark, Wyo. The road that led him to a permanent place in gunmaking history was far from a typical one.
Review: Rock Island Armory TM22
In 2021, Rock Island Armory shook things up in the defensive-pistol world when it launched the aluminum-based STK100, and in 2022 the company continues its commitment to “Total Metal” firearm construction with the TM22 rimfire rifle.


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The cast of the sixth and final season of the Emmy Award-winning Netflix series The Crown has been photographed on set — and we’re getting our first glimpse of the new Kate Middleton and Prince William.
Chronicling the epic saga of the British royal family, the forthcoming season will follow the early days of the Prince and Princess of Wales’s love story. The couple met while studying at the University of St. Andrews in Scotland, circa 2001, before beginning to date in 2003. Portrayed by Ed McVey and Meg Bellamy, the behind-the-scenes shots capture the actors filming at the college — and they draw an uncanny resemblance to the pair of young royals.
The show is currently in production after filming was halted in September following the death of Queen Elizabeth II out of respect for the late monarch. “As a mark of respect, filming on The Crown was suspended today,” Netflix said in a statement acquired by the Hollywood Reporter at the time. “Filming will also be suspended on the day of Her Majesty the Queen’s funeral.”
That same month, the streamer announced The Crown had found their Prince William and Kate Middleton for the series’ sixth season. According to Deadline, producers casted two actors to play William throughout time periods. Rufus Kampa will assume the role of Prince William at age 15 — the age of the royal when his mother Princess Diana died in a tragic car accident.
Kampa will be replaced later in the season by McVey, who will portray the former Duke of Cambridge in his late teen and early adult years, during his courtship with a young Kate Middleton, set to be played by Bellamy.
The Queen was being previously portrayed by Claire Foy in the first two seasons, and Olivia Colman in seasons 3 and 4. Next, Harry Potter actress Imelda Staunton played Queen Elizabeth in the series’ fifth season and will continue in season 6.
“I have loved watching The Crown from the very start,” said Staunton in a statement. “As an actor it was a joy to see how both Claire Foy and Olivia Colman brought something special and unique to Peter Morgan’s scripts. I am genuinely honored to be joining such an exceptional creative team and to be taking The Crown to its conclusion.”
The series introduced a young Lady Diana in season 4, with Emma Corrin starring as the “People’s Princess” opposite Josh O’ Connor’s Prince Charles. Elizabeth Debicki took the reins as Princess Diana for seasons 5 and will continue for 6, with Dominic West as Prince Charles.
Jonathan Pryce will continue to follow Tobias Menzies as Prince Philip, while Lesley Manville will continue in her role as Princess Margaret, following Helena Bonham Carter.
Season 5 highlighted the royal family in the early-to-mid 1990s, likely focusing on the Prince and Princess of Wales’s failing marriage, separation in 1992 and subsequent divorce in 1996.
The final season of The Crown is set to hit Netflix later this year. And we can. not. wait.
Stay tuned for further developments.


by Joe Bollig
LENEXA — The message was strong and the style was what the speaker, Richard Lane Jr., called “Batholic” — Baptist African-American preaching style with Catholic substance.
“We have to stand up for what we believe in,” he thundered. “We have to stand up for what God has given us!”
Lane, a convert and an evangelist from St. Alphonsus Liguori Parish in St. Louis, was one of two main speakers at the 14th annual Men Under Construction men’s conference on Feb. 27 at St. James Academy in Lenexa.
Society is experiencing many evils because the devil is attacking humanity at the core of the family — the fathers, he said.
“Well, who is the head of the household?” he shouted as he swept his arm dramatically over the men. “It is you, brothers! It is you! And the devil is kicking our behinds each and every day.”
“Ouch!” someone called out from the more than 650 men seated before Lane.
“Amen! Ouch,” Lane replied. “But we don’t know how to fight back, brothers. A lot of us continue to live in fear! Every day!”
Too many men are finding solace in sin: alcohol abuse, fornication, and pornography.
“It’s killing us, brothers!” he shouted. “It’s killing you! And it’s killing your families!”
Few of the men in the chapel and commons of St. James Academy had ever personally experienced someone like Lane before, and they sat in rapt attention.
The second speaker of the day, former mobster Michael Franzese followed Lane with his own story of how he became a key man in the Colombo crime family of New York, and gave it all up when he converted to Christ — the ideal man.
“I grew up in that life,” said Franzese. “I was always told, ‘You’ve got to be a man’s man, Michael; you’ve got to emulate a man.’”
And so Franzese began to emulate some of the most ruthless and dangerous men in organized crime, until he found a new model of manliness.
“But then, when I started to read about Jesus — sometimes we forget that he was a man, but I didn’t,” he continued. “I was so in tune with the manliness, the manhood of Jesus, I was blown away by him. I said, ‘My gosh, this is the man I want to emulate in my life.’ …The way he stood in front of Pilate, knowing that he was innocent. Kept his mouth shut. Knew he had a job to do and was going to take it on the chin for everyone. There isn’t a mob guy in the world who’s going to do that.”
Lane and Franzese set the tone for what was a very successful event, said Dan Spencer, chairman of Men Under Construction.
“It was very good,” he said. “Our speakers were both very passionate and connected well with the attendees. And our breakout sessions did pretty well.”
This year’s event had a few firsts, said Phil Hernandez, a breakout session leader and Men Under Construction board member.
This was the first year the event was held at St. James Academy in Lenexa, and the first time the event was promoted on secular radio stations. It was also the first time the organizers planned eight breakout sessions instead of a large workshop, and it was the first time “parish captains” were used to promote the event.
“I thought it was phenomenal,” said Hernandez. “I really felt that the new venue, the speakers, the new format for the actual event itself — with speakers in the morning and breakouts that addressed real topics that men have to face every day — was a combination that touched hearts. [Richard] Lane said, ‘I’m trying to reach and save souls,’ and I think we saved a soul or two, or at least energized a few. It was a pretty special day.”
The crowd was larger than what the organizers expected — the total boosted by walk-in attendees — so a moveable wall was opened between the chapel and a commons area, and more food had to be hurriedly prepared for lunch.
Tim Ruoff, a member of Mother Teresa of Calcutta Parish in Topeka, arrived in a chartered bus with 30 other parishioners. He also brought his son Josh, age 15.
“I think he was really moved by some of the stories shared, especially by Michael Franzese,” said Ruoff. “Michael did a breakout session with the young people. I don’t know exactly what he said, but Josh said it really moved him.”
Rich Bartlett, a member of the Church of the Ascension in Overland Park, made the day a multigenerational affair. He attended with his 16-year-old son Alec and his 75-year-old father Dick — the first time for each of them.
“I thought it would be a good opportunity to spend some quality time together,” said Bartlett. “It was sold as a really well put-together venue to have fellowship with other men, and for fathers and sons. That was the expectation I came in with and, man, did I come out with a great experience.”
The speakers couldn’t have been better, he said, because their message resonated at all age levels. Also, the variety of activities gave the Bartletts several opportunities to share special experiences together.
“The beauty was that there wasn’t just one moment,” he said. “I felt very comfortable opening up in a multitude of ways. It seemed to open up dialogue between a dad, a grandfather, and a 16-year-old boy. So, it just wasn’t one moment. It was the whole day.”
The day began with the two speakers and was followed by opportunities to receive the sacrament of reconciliation. The lines were long even though several priests were available.
After lunch, the attendees went to two of eight breakout sessions, where speakers addressed particular topics. Afterward, the men returned to the chapel for eucharistic procession and adoration led by Archbishop Joseph F. Naumann. The event closed with a final blessing by the archbishop.
The organizers of Men Under Construction are planning for next year’s event to be even better to celebrate its 15th anniversary.
They already have allies in attendees like Bartlett.
“I will be their biggest advocate,” he said. “I’ve sent e-mails to several of my Catholic buddies who stayed on the sidelines, saying, ‘You’ve go to go next year.’ Several are kicking themselves for not going. We’ll be rallying for a lot of folks to go next year.”