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AU2006341380B2 - Light activated antiviral materials and devices and methods for decontaminating virus infected environments - Google PatentsLight activated antiviral materials and devices and methods for decontaminating virus infected environments Download PDF
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation; Therapies using these preparations
- A61K41/0009—Inactivation or decontamination of a medicinal preparation prior to administration to the animal or human, e.g. : inactivation of viruses or bacteria for vaccines, sterilisation by electromagnetic radiation
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine, rifamycins
- A61K31/40—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine, rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil
- A61K31/409—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine, rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil having four such rings, e.g. porphine derivatives, bilirubin, biliverdine
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine, rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine, rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/47—Quinolines; Isoquinolines
- A61K31/473—Quinolines; Isoquinolines ortho- or peri-condensed with carbocyclic ring systems, e.g. acridines, phenanthridines
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation; Therapies using these preparations
- A61K41/0009—Inactivation or decontamination of a medicinal preparation prior to administration to the animal or human, e.g. : inactivation of viruses or bacteria for vaccines, sterilisation by electromagnetic radiation
- A61K41/0019—Inactivation or decontamination of a medicinal preparation prior to administration to the animal or human, e.g. : inactivation of viruses or bacteria for vaccines, sterilisation by electromagnetic radiation by UV, IR, Rx or gamma rays
WO 2007/114843 PCT/US2006/043919 DESCRIPTION LIGHT ACTIVATED ANTIVIRAL MATERIALS AND DEVICES AND METHODS FOR DECONTAMINATING VIRUS INFECTED ENVIRONMENTS 5 CROSS REFERENCE TO RELATED APPLICATION This application is related to and claims priority to U.S. Provisional Application Serial No. 60/788,010, filed March 31, 2006 and entitled Light Activated Antiviral Materials and Devices and Methods for Decontaminating Virus 10 Infected Environments. The disclosure of said provisional application is specifically incorporated by reference in its entirety herein. BACKGROUND OF THE INVENTION 1. Field of the Invention 15 This invention relates to the field of light-activated antiviral materials, systems and devices, methods for manufacture thereof and the use of such materials and devices to decontaminate viral infected environments and prevent viral infections. More specifically, the invention relates to the attachment of singlet oxygen generating materials and compounds to surfaces such as fabrics, particles, solid surfaces and the 20 like to provide an antiviral environment through generation of singlet oxygen by illumination of such surfaces to generate singlet oxygen which functions to inactivate viruses, and to a certain extent, bacteria. 2. Discussion of the Relevant Art 25 Dyes such as the porphyrins, the fluoresceines, the phenothiaziniums, and the phthalocyanines, as well as others listed in Wilkinson, Helman et al. 1995, which is incorporated by reference herein in its entirety, and others not listed by Wilkinson, Helman et al are known as materials that release singlet oxygen upon exposure to light. In particular, phthalocyanine, aluminum phthalocyanine, protoporphyrin IX 30 and zinc-protoporphyrin IX, which are well known materials, generate singlet oxygen when dispersed in free form and are known to be effective as antimicrobial agents. 1 WO 2007/114843 PCT/US2006/043919 In the past, it was thought that grafting of light-activated antimicrobial material, such as protoporphyrin and zinc-protoporphyrin to surfaces such as nylon films and fibers, would serve to preserve the films and fibers and prevent the transmission of disease through prevention of the transmission of bacterial infectious agents. One 5 such approach is described in an article entitled "Grafting of Light-Activated Antimicrobial Materials to Nylon Films" by Jennifer Sherrilll, Stephen Michielsen, and Igor Stojiljkovic, published on November 20, 2002, in Journal of Polymer Science, Part A Polymer Chemistry, Vol. 41, pages 41-47, 2003, the disclosure of which is specifically incorporated in its entirety by reference herein. That article 10 describes various methods for respectively: 1) synthesis of various derivatives of protoporphyrin; and 2) grafting such derivatives such as PPIX-ED or Zn-PPIX-ED to PAA-grafted nylon films. In a later article entitled "Porphyrin-Based, Light-Activated Antimicrobial 15 Materials" by Jadranka Bozja, Jennifer Sherrill, Stephen Michielsen, and Igor Stojiljkovic, published on June 11, 2003 in Journal of Polymer Science, Part A Polymer Chemistry, Vol. 41, pages 2297-2303, 2003, the disclosure of which is also incorporated in its entirety by reference herein, the antimicrobial properties of the aforementioned protoporphyrin grafted nylon fibers as tested were described. The 20 fibers were shown to be somewhat active against Staphylococcus aureus and Escherichia coli, depending upon light intensity to which the fibers were exposed as well as exposure time. While some effectiveness against such bacteria was shown, later tests have shown 25 that the antibacterial effect of such grafted or bound protoporphyrin materials may not be sufficiently effective against bacteria to be of effective use when attempted in the manner discussed in the article. Further tests have shown that when the protoporphyrin materials are bound to fabrics as disclosed therein, that there may be an insufficient amount of singlet oxygen generated due to lack of effective exposure 30 of the dyes to light to be fully effective against such bacteria. Thus, although it is known that protoporphyrin and other like dyes can be effective in a free form when exposed to light, and in that form generate sufficient singlet oxygen to be effective 2 WO 2007/114843 PCT/US2006/043919 against selected bacteria, in contrast, when the dye is bound to fabrics, broad effectiveness against bacteria declines substantially. It is desirable to develop methods and systems to address the spread of influenza. 5 Influenza is only one of many viruses that are spread by aerosolized droplets when infected people cough or sneeze. It spreads rapidly throughout the world in seasonal epidemics. The World Health Organization estimates that influenza epidemics cost the US economy $ 71-167 billion per year. It is also estimated that 250,000-500,000 people die every year from influenza epidemics. Current fears of a pandemic due to 10 the avian H5N1 strain of influenza (the "bird flu") illustrate that we have still not found a viable way of preventing pandemics. Although vaccination has been shown to be effective in reducing the occurrence and severity of influenza infections, because of rapid variation in the antigenic properties of circulating viruses, new vaccines have to be produced on annually. Time constraints and reliance on growth 15 of vaccine stocks in eggs means that only limited supplies of vaccine are available in any single flu season. There are only two classes of pharmaceuticals that are effective against influenza which inhibit virus uncoating and virus release, and recent studies indicate that these drugs are losing their effectiveness as the virus develops resistance. The development of new drugs to fight viral infections has 20 proven to be extremely difficult. In addition, the cost of the current methods for preventing or treating viral infections is prohibitive in many regions of the world, including those regions where many of these infections are believed to originate. Therefore, a new, low cost approach to preventing the spread of viral infections in general, and influenza in particular, would be extremely beneficial. 25 One system used against viruses involves photodynamic therapy. Photodynamic therapy in /general has been shown in the past to be able to inactivate many enveloped viruses, including HIV through the production of singlet oxygen, Ag. The mechanism of inactivation of enveloped viruses with the use of Rose Bengal or 30 hypericin has been investigated and it was found that singlet oxygen crosslinked protein G on the surface of VSV, thus inhibiting viral fusion. A similar mechanism inactivates other like viruses. Virus inactivation is proportional to the. intensity of light used. Both materials are known to produce singlet oxygen on exposure to light 3 and both were ineffective in the dark. It 'as shown that singlet oxygen produced thermally from the decomposition of poly(1,4-methyl-t-viiiylnaphthalene- 1,4 endoperoxide) also inactivated enveloped iruses, confirming that singlet oxygen was the active material. However, to date it has not been known how to effectively 5 apply photodynamic therapy in useful meth ds, articles and systems. To understand the principle of operation the d es describeO herein, it is noted that the ground state of normal oxygen has its two most energetic electrons arranged with parallel spin in a -r molecular orbit to produce a state that is described 10 as a spin triplet state represented by the s ctroscopic notation Y. Situated 95 kJ above this state is a state where the elec ons in the Ag molecular orbital have opposite spin yielding a spin singlet state Ag. It is this excited state that is commonly referred to as singlet oxygen. one effective way of generating singlet oxygen is the use of metal substituted porph rin, phthalicyanine and other 15 molecules as described above and hereafteriwhich have been ir tegrated as reactive, visible light activated photocatalysts within chemical/biological agent resistant flexible polymer barrier coatings which have been previously developed. Such photocatalysts are large ring compounds that have strong absorption in the visible region of the spectrum and can be blended t> match required color specifications. 20 BRIEF SUMMARY OI THE INVENTION In one aspect the invention relates to a m thod of inhibiting growth of viruses in vitro, comprising: 25 attaching through covalent bondi g, through a me iator polymer, an effective amount of a dye, selected from one of reactive dyes 'nd dyes containing reactive functional groups, onto a substrae, said compositio: of said dye being further characterized by having the ability to absorb light kn a predetermined spectrum and intensity range to thereby produce singlet oxygen in the presence of 30 an oxygen containing atmosphere, upon atsorptiou of light in said predetermined spectrum range, in an amount effective ;o inactivate viruses when in contact therewith, and wherein said mediator polymer is coated on said substrate in a 4 38390702 (GHMaftmo) P7918SAu thickness which adds less than 0.5% to th weight of said substrate and increases the available reactive sites for said dye by heater an 100 fold; and contacting viruses to be inactivated with said substrate having said composition adhered thereto in the presence of oxygen and light in said 5 predetermined spectrum and intensity rang 9 . Also disclosed is an article of manufacture capable of inhibiti g growth of viruses in vitro comprising: a substrate, wherein the substrate is surface; and 10 an effective amount of a composite n of a dye selected from at least one of reactive dyes and dyes containing reacti' e functional groups, attached to said substrate through covalent bonding, throu1 a mediator polymer, said dye being further characterized by having the ability to absorb light in a predetermined spectrum and intensity range and to produce singlet oxygen in the presence of an 15 oxygen containing atmosphere, upon absorption of light ofj said predetermined spectrum and intensity range, in an amoun effective to inactiiate viruses when in proximity thereto, wherein said mediator olymer is coated on said substrate in a thickness which adds less than 0.5% to- the weight of said substrate and increases the available reactive sites for said dye by greater than 100 fold! 20 Also disclosed is a method of manufacture an article capable of inhibiting growth of viruses in vitro, comprising providing a substrate, wherein the siibstrate is a surface;I attaching through covalent bondi g, through a m diator polymer, an 25 effective amount of a composition of a dye o said sbstrate, said dye selected from at least one of a reactive dye and dyes containing reactive functional groups, said dye being further characterized by having the ability to absorb light in a predetermined spectrum and intensity rai ge to roduce singlet oxygen in the presence of an oxygen containing atmos ere, upon absorpt on of light of said 30 predetermined spectrum and intensity ran e, in an amount elective to inactivate viruses when in proximity thereto, wherein aid mediator polymer is coated on said substrate in a thickness which adds less th 0.5% to the wei t of said substrate and increases the available reactive sites fo said dye by greater than 100 fold. 5 =&90702 (GMMafer3) P79189.AU In a preferred aspect, the dyes are at least two different dyes, nd more preferably three, each selected to be effective in- generating singlet oxyg n when exposed to light of a different spectrum range from the ther d es. 5 In a yet more specific aspect the dye is of tle follow ing basic structure: R R R N R Where R is a hydrogen, a hydroxyl, a ca boxyli acid, an alyl, an amino or a 10 substituted amino group or other group ob rious to one skilled in the art. At least one of the R's being an amino, hydroxyl, ca boxyli9 acid, or otl er reactive group. More specifically, the dye is one of acridne yellow G, proflavin and acroflavin. Most preferably, the dye is acridine yellow . 15 In a yet still more specific aspect the substrate can be fibers and fabrics, as well as other types of surfaces. For purpose of this disclosure, it is noted Ohat term "attached"! is meant molecular 20 bonding, coating, impregnation, adsorption rld other forms of attachment as will be apparent to those of ordinary skill. In addition, by substrate is meant at least one fiber, a fabric, or other types of surfaces suh as wills, wall co erings, paper, paint, plastic, non-woven fabrics, etc., and generally any surface to Which dyes described herein can be attached as will be readily apparent to those of ordinary skill. 25 3839 070 2 GHI~atta) P79189-AU WO 2007/114843 PCT/US2006/043919 In one aspect, in accordance with the invention, it has been discovered that a method of binding protoporphyrin and other singlet oxygen generating materials to fabrics can be effectively practiced in a manner in which sufficient singlet oxygen can be generated such as to be effective in certain unexpected and untried applications. 5 More specifically, while proporphyrin and singlet oxygen generation in bound form was in the past considered to be somewhat effective against selected types of bacteria, it has unexpectedly been discovered that such materials when modified in accordance with the invention described herein, can be bound to materials such as fabrics, generate sufficient singlet oxygen to be effective against viruses. It has been 10 discovered that materials prepared in accordance with the invention described herein can have the effect of neutralizing viruses of the type that are "enveloped", such as influenza, vaccinia, and the like. While the effectiveness of porphyrin and singlet oxygen has been demonstrated 15 against bacteria when the porphyrin is in free form, in bound form it is less effective against bacteria. Since the mechanism by which the bacteria are killed by singlet oxygen is substantially different from what occurs in an environment containing viruses, and the operation on viruses due to their substantially different nature than bacteria, the effectiveness of singlet oxygen generating dyes against viruses as 20 described herein is completely different, unexpected and unanticipated. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS Figure 1 is a graph showing the spectrum and relative intensity of light reflected off 25 of fabric containing certain dyes on a fabric in accordance with the invention. Figure 2 is a graph illustrating virus inactivation by a nylon fabric having poly(acrylic acid) attached thereon, and a fabric from example 7. Figure 3 is a graph illustrating virus inactivation by a fabric having azure A or Rose Bengal dyes attached thereon; and 30 Figure 4 is a graph illustrating virus inactivation by a fabric having acridine yellow G attached thereon. 6 WO 2007/114843 PCT/US2006/043919 DETAILED DISCUSSION OF THE INVENTION The development of the invention is based in part on recent events that have led to 5 new concerns about biowarfare and bioterrorism. Because of the potential range of biological agents that could be used, a non-specific decontamination system is desirable. Of particular interest herein are materials whose surfaces have been modified to be self-decontaminating and self-regenerating. Other beneficial requirements are that the surface treatment be very light weight. These coatings are 10 based on Light Activated Antiviral Materials, i.e.,LAAM that have been developed. The LAAM coatings have the further attribute that they are able to be color matched to nearly any color desired. The invention addresses in part surface modification. In one embodiment of a 15 coating developed as part of the invention an about 10 to about 20nm, and typically about 5-15nm, and most typically about 10 nm thick mediator or amplifying polymer is bonded to the surface of fibers. Then photo-active agents are grafted to this mediator polymer. By the term mediator or amplifying polymer is meant a polymer that attaches or binds to reactive sites on the surface and creates many more 20 reactive sites for attachment. It is, in effect, a surface site amplifying material. This increases the available photo-active agents by greater than 100 fold, while adding less than 0.5 wt % and typically less than 0.1 wt % to the substrate. The amount is net by weight of active reagent versus the weight of the substrate. These photo active agents absorb visible light and transfer the energy to oxygen in the air to 25 generate singlet oxygen, which has been shown to destroy certain microbes. Since the photo-active agents are organic dyes, it is possible to simultaneously match specification colors. As already noted, there has long been an interest in the development of self 30 decontaminating treatments for hard and soft surfaces that do not contribute significantly to weight nor require transport or handling of decontamination supplies, as well as which have zero toxic effluents. As described herein, a self 7 WO 2007/114843 PCT/US2006/043919 decontaminating surface based on the synthesis of singlet oxygen from photo-active organic dyes has been developed. Any treatment designed with the aim of decontamination must be effective against 5 as wide a variety of agents as possible, and not targeted against specific features of an individual organism. Decontamination of microbes is typically carried out by irradiation, exposure to solvents or exposure to agents that cause oxidative damage to biological macromolecules. These latter treatments include bleach and gases such as ethylene oxide and chlorine dioxide. In the environments where human beings 10 are present, use of irradiation either with gamma rays or high intensity UV irradiation is undesirable, as is the exposure of personnel to organic solvents and noxious gases. However, the Light Activated Antiviral Materials, LAAM, technology discussed in a subsequent paragraph results in the in situ production of singlet oxygen, which is one of a number of reactive oxygen species that cause 15 oxidative damage to lipids and proteins. In proteins, target amino acids are Trp, His, Tyr, Cys and Met. This technology has also been shown to be somewhat effective against gram positive bacteria. This suggested the incorporation of LAAM technology into the design of materials will confer the substantial benefit of decontamination of a broad range of biological agents. However, further testing has 20 shown that when such LAAM materials are bonded, as developed with the invention, such materials have been shown to be of limited effect against Gram positive bacteria. However, as further modified herein, such dyes bonded to surfaces such as fabrics have been shown to be highly effective against enveloped viruses. 25 In accordance with the invention, there have been developed light activated antiviral materials, LAAM. These materials absorb visible light to convert oxygen from the air or dissolved in water to Ag oxygen. LAAMs have been developed for treating individual fibers, yams, fabrics, particles, or other surfaces. In one embodiment, 30 protoporphyrin IX, (PPIX), and zinc protoporphyrin IX, (Zn-PPIX), have been chemically bonded for example, as discussed in the aforementioned article entitled "Grafting of Light-Activated Antimicrobial Materials to a Nylon Film" to the surface of nylon films and fabric using poly(acrylic acid), PAA, as a mediator 8 WO 2007/114843 PCT/US2006/043919 polymer. PAA is first dissolved in water and grafted onto the nylon surface in the presence of coupling agents. The PAA could not be removed in multiple washings. Next, an amide bond was formed between the carboxylic acid groups in PPIX and the amino groups in ethylene diamine. Finally, these derivatives were grafted to 5 PAA, again by forming amide bonds, this time between the other end of the ethylene diamine and the acid groups in PAA. In this way, it is possible to graft multiple molecules to a single PAA molecule, which is attached to the nylon surface. Without the PAA acting as a mediator or amplifier to bond PPIX, only one PPIX molecule could be attached per surface nylon molecule. In other words, the PAA 10 mediator increased the amount of PPIX or Zn-PPIX on the surface. Fabrics made using this treatment were able to destroy to a certain extent Gram positive bacteria and more effectively enveloped viruses. The essential features of this approach are that the LAAM are composed of suitable dyes that absorb UV/visible/near infrared light. The excited state of the dye exchanges its spin and energy with oxygen from 15 the air to produce Ag oxygen. The LAAM dye must resist photobleaching and photo-oxidation for the intended duration of use. A high quantum yield is desirable. The LAAM dye is preferable such that it is able to be grafted to a suitable mediator polymer or capable of conversion to a form which can be grafted to a suitable mediator polymer. Finally, the modified surface should have the desired colors, for 20 example, for military or other applications. Fortunately, there are a large number of dyes to select from, so that finding a suitable LAAM dye is not difficult. Furthermore, LAAMs covering the entire range of colors desired are readily achieved. 25 In one preferred aspect, at least two and preferably three dyes are employed. The dyes are selected to cover the spectrum from near infrared to UV light to thereby be effective against viruses in all light conditions. If only one dye is used, dyes having the previously claimed basic structure are employed because of the high and unexpected level of effectiveness against viruses which was not found with other 30 dyes. In a most preferred aspect the single dye is acridine yellow G. Of course, the dyes having said formula, including acridine yellow G can also be combined with other dyes to cover the full spectrum described. 9 WO 2007/114843 PCT/US2006/043919 Since most typically in excess of about 75% by weight and more typically in excess of 90%, of all of the photo-active material is on the surface, these LAAMs add very little weight to the finished products. They are self-regenerating because they use oxygen from the air and light, either natural or artificial, to replenish their 5 decontamination material. In addition, there are no effluents since the active ingredient, Ag oxygen, has a lifetime of less than about 10 msec before it reverts back to ground state oxygen, which is present in air everywhere. In addition, it is not corrosive nor does it produce salts. Thus, LAAMs provide a highly desirable decontamination means. 10 One first step in making a LAAM fabric surface is to attach LAAM material to the surface. This is accomplished by grafting suitable photo-active materials to the surface, i.e. to form a LAAM on the surface. Reactive porphyrin and phthalocyanine dyes are examples of dyes which can be chemically grafted upon the 15 surfaces and have high quantum yields for producing Ag oxygen. Specifically, fabrics of polyaramid, polyamide or polyesters such as poly(ethylene terephthalate) fibers are used as surfaces. Onto these fibers, there is adsorbed and grafted poly (acrylic acid), PAA, to form PAA-g-fabric. Next, protoporphyrin IX, zinc protoporthyrin IX, phthalocyanine or other dyes are grafted to the PAA-g-fabric as 20 described by the aforementioned article entitled "Grafting of Light-Activated Antimicrobial Materials to a Nylon Film." The resulting LAAM fabric was tested for its ability to (1) produce Ag oxygen, and (2) to render various viruses harmless. Each of these tests is described in more 25 detail hereinafter. Because of the hundreds of dyes that are known to efficiently produce Ag oxygen, there is no undue difficulty in accomplishing this task. Dyes with high quantum yields for producing singlet oxygen may be selected from reference literature. Dyes known to have a high singlet oxygen quantum yield 30 include the porphyrins, the fluoresceines, the phenothiazines, the xanthenes and the phthalocyanines. These dyes cover nearly all of the visible spectrum as well as the near infrared and the near ultraviolet. The dyes are selected based on the ease with which they can be grafted to poly(acrylic acid), poly(ethylene imine) or other 10 WO 2007/114843 PCT/US2006/043919 mediator polymer. In particular, dyes are selected containing alkene, carboxylic acid, hydroxyl, amino , thiol and other reactive groups. Figs. 2, 3 and 4 show effectiveness of specific dyes against virus. Acridine yellow 5 G shows unexpected and very high virus inactivation with low light illumination levels. The following is a representative listing of the dyes, but the listing is not limited to these dyes as will be readily apparent to those of ordinary skill. 10 Suitable dyes are those that generate singlet oxygen upon exposure to light and that contain chemical moieties that allow them to be chemically bonded to the surface or to the mediator polymer. These include many of the dyes listed by Wilkinson, Helman and Ross (J. Physical Chem. Ref. Data, Vol 24, pp 663 - 1021) including 15 protoporphyrin IX, zinc protoporphyin IX, Rose Bengal, thionin, Azure A, Azure B, Azure C, proflavine, acriflavine, vinyl anthracene, 1-amino-9,10-anthraquinone, 1,5 diamino-anthraquinone, 1,8-diamino-anthraquinone, 1,8-dihydroxy-9,10 anthraquinone, 1 -hydroxy-9,1 0-anthraquinone, 1,4,5,8-tetraamino-9,10 anthraquinone, 1,4,5,8-tetrahydroxy-9,10-anthraquinone, Eosin B, Eosin Y, Phloxin 20 B, fluorescein, Erythrosin, tribromo-fluorescein, hypericin, kynurenic acid, riboflavine, chlorophyll a, chlorophyll b, coproporphyrin I, coproporphyrin II, coproporphyrin III, Ga protoporphyrin IX, clorin e6, proflavin, acroflavin, acridine yellow G, toluidine blue, anthracine derivatives, anthraquinones, tetracarboxyphthalocyanine, Sn tetracarboxyphthalocyanine, Al 25 tetracarboxyphthalocyanine, Ge tetracarboxyphthalocyanine, 5-amino-etioporphyrin I, chlorin e6, as well as the zinc and aluminum derivatives of the above listed porphyrin and phthlocyanine derivatives, or other dyes that will be obvious to those skilled in the art. In addition, many other dyes that generate singlet oxygen upon illumination can be used provided that they can be attached to the surface or to a 30 mediator polymer. In addition to the above dyes, as shown in Figure 4, acridine yellow G has shown unexpected efficiency in virus inactivation. 11 WO 2007/114843 PCT/US2006/043919 The LAAM materials developed were tested for their ability to retain their antiviral activity. The biological tests are described hereinafter. 5 When the LAAM was a fabric, a chemical trapping method was used to measure the amount of singlet oxygen generated under different illumination conditions. Furfuryl alcohol is known to react rapidly with singlet oxygen. An aqueous solution of furfuryl alcohol is added to a sealed circulation system containing the fabric sample and oxygen saturated water. The dissolved oxygen concentrations were 10 measured during illumination. The dissolved oxygen concentration decreased as singlet oxygen was photochemically generated and reacted with furfuryl alcohol. Choice of agents and biological testing: 15 Testing initially focused on bacteria and poxviruses. Bacillus subtilis served as a model for decontamination of Gram positive bacteria. As a model for poxviruses, we used vaccinia virus. The vaccinia virus can be safely handled in a normal micobiological laboratory and does not require any special containment facilities. 20 In accordance with the invention, it is effective against Yersinia pestis, yellow fever (for the flavivirus encephalitis viruses), sindbis virus (alpha virus encephalitis virus), avian infectious virus (corona diseases such as SARS) and parainfluenza virus (the highly pathogenic nipah and hendra viruses.) 25 Having described the invention generally, the following are specific examples showing manufacturing and use of specific embodiments of the invention for inactivating viruses. Example 1: 30 Virucidal activity of Zn-protoporphyrin IX (Zn-PPIX) grafted onto nylon (pieces of cloth, size 1 by 1 cm) was tested against infectious vaccinia viruses. The Zn-PPIX grafted nylon fabric was made as follows. Poly(acrylic acid) (PAA) was dissolved in water at a concentration of 1.4 g/L. A piece of nylon fabric was immersed in 35 ml 12 WO 2007/114843 PCT/US2006/043919 of this solution. 10 ml of an aqueous solution of 4-(4,6-dimethoxy-1,3,5-triazin-2 yl)-4-methylmorpholinium chloride (DMTMM) was added (20 g/L). The solution was gently shaken for 1 hour, the fabric was removed from solution, rinsed with water and dried. The fabric formed had PAA grafted onto its surface. Next, 0.1 g of 5 Zn-PPIX, 0.2 g of DMTMM, and 100 p.L of ethylene diamine were dissolved in 120 mL of water and stirred for 30 minutes. At this point, the PAA-grafted nylon fabric was placed in this reaction mixture. Excess solution was squeezed out and the fabric dried and cured at 120 0 C for 40 minutes. The resulting Zn-PPIX nylon fabric was obtained by evaporating the water to dryness. This fabric was then cut into 1 cm by 10 1 cm pieces for antiviral activity testing. For the assay of the effect on vaccinia virus infection, a plaque assay was used. This assay is able to determine how many infectious particles remain after LAAM light treatment. 15 BSC40 cells were used. The following samples were tested: 1) 20pl of virus stock (conc. 1X10 6 ) was added to Zn-PPIX treated fabric, 2) 20ptl of virus alone, 3) 20ptl of wash media, samples were illuminated for 30 min. at 60,000 Lux., 4) 20pl of virus stock on Zn-PPIX treated fabric was kept in the Petri dish wrapped in Al foil 20 as a control. After 30 minutes, cells were infected. Two days after infection, medium was removed, cells were stained, and the number of plaques was counted. Results are as follows: Virus on Zn-PPIX treated fabric (illuminated) - no plaques 25 Virus alone: in 10-2 dilution 70 plaques Virus on Zn-PPIX treated fabric (control, dark): in 10-2 dilution - 40 plaques Wash media alone - no plaques Example 2: 30 With respect to bacteria with light exposure as described above (Light at 60,000 Lux and Zn-PPIX treated fabric), the grafted materials were somewhat effective on Bacillus strains. 13 WO 2007/114843 PCT/US2006/043919 Two Bacillus strains were used in experiments: Bacillus cereus strain by BGSC code 6A5 (original code: ATCC14579), description; wild type isolate, type strain of B. cereus. 5 Bacillus thuringiniensis, BGSC No. 4A1; original code NRRL-B4039; description: wild type isolate. We tested the extent to which Zn-PPIX treated fabric was able to inactivate Bacillus cereus and B. huringiensis spores to germinate and produce viable vegetative cells. 10 1 cm by 1 cm pieces of LAAMs (Nylon, PPIX, and Zn-PPIX) were immersed in fresh spore dilution (ABS 5 so0.3) and then exposed to light. The source of light was a tungsten lamp. Light intensity under 60,000 Lux did not have an effect on spores. At 60,000 Lux during the 30 minute exposure, only Zn-PPIX treated fabric had an effect on spores: 20.16% of spores of strain 4A1 was able to produce viable 15 vegetative cells, and from strain 6A5-23.14%. Control cultures were left in the dark for the same amount of time (30 min.) and did not show any reduction in the number of the spores. PPIX and nylon had limited effect on spores at 60,000 Lux. Example 3 20 Cerex Suprex HP spunbonded nylon nonwoven (DuPont) with a basis weight of 45 gsm. 2.0 g of poly(acrylic acid) of molecular weight 450,000 was dissolved in 500 ml of water. The nonwoven fabric was pulled through this solution and squeezed between padder rolls to a wet pickup of 135% wt/wt of fabric. The treated fabric was allowed 25 to sit for two days covered with aluminum foil to prevent water evaporation, then rinsed with fresh water six times. Next, an aqueous solution of 4-(4,6-dimethoxy 1,3,5-triazin-2-yl)-4-methylmorpholin-4-ium chloride, DMTMM, consisting of 0.41 g DMTMM in 250 ml water was made up and the treated fabric pulled through this solution and squeezed to remove excess solution. This fabric was allowed to sit 30 covered with aluminum foil for two hours and rinsed 6 times. 14 WO 2007/114843 PCT/US2006/043919 Example 4 A portion of the fabric made in Example 3 was treated with Acridine Yellow G as follows. 0.185 g of Acridine Yellow G and 0.364 g of DMTMM were dissolved in 250 ml of water. The fabric of example 3 was pulled through this solution and 5 excess was squeezed out between padder rolls. The fabric was allowed to sit for 24 hours whereupon it had a vibrant yellow color. Unreacted dye was extracted by rinsing until no more color was observed in the rinse water. Example 5 10 A portion of the fabric made in Example 3 was treated with Azure A as follows. 0.231 g of Azure A and 0.329 g of DMTMM were dissolved in 250 ml of water. The fabric of example 3 was pulled through this solution and excess was squeezed out between padder rolls. The fabric was allowed to sit for 24 hours whereupon it had a pale blue color. Unreacted dye was extracted by rinsing until no more color was 15 observed in the rinse water. Example 6 A portion of the fabric from Example 3 was treated with Rose Bengal as follows. First, Rose Bengal was derivatized to add an amino linkage group by dissolving 0.47 20 g Rose Bengal in 2 ml of ethylene diamine and 6 ml of water. This solution was refluxed for 30 minutes, and rotoevaporated to dryness to remove excess ethylene diamine. The product was a deep red, viscous liquid. Then, 1.99 g of poly(acrylic acid) was dissolved in 500 ml water. The fabric of 25 example 3 was pulled through this solution and squeezed between padder rolls to a wet pickup of 135% wt/wt of fabric. The treated fabric was allowed to sit for 30 minutes covered with aluminum foil to prevent water evaporation. 0.346 g DMTMM was dissolved in 250 ml of water and the fabric was pulled through this solution, excess solution squeezed out with a padder and allowed to sit covered for 30 30 minutes. One half of the Rose Bengal amine derivative was dissolved in 250 ml of water, the treated fabric pulled through this solution, excess solution squeezed out on a padder and the fabric allowed to sit for 30 minutes. Next, 0.16 g DMTMM was dissolved in water and padded onto the fabric as described previously. The fabric 15 WO 2007/114843 PCT/US2006/043919 was allowed to sit for 30 minutes, then rinsed with water until no further color was seen in the rinse water. The treated fabric was pink. Example 7 5 A portion of the fabric from Example 3 was treated with Rose Bengal, Acridine Yellow G, and Azure A dye mixture as follows. One half of the Rose Bengal amine derivative described in Example 5 along with 0.049 mg Azure A, and 0.051 mg Acridine Yellow G were dissolved in 250 ml of water. 10 Then, 1.99 g of poly(acrylic acid) was dissolved in 500 ml water. The fabric of example 3 was pulled through this solution and squeezed between padder rolls to a wet pickup of 135% wt/wt of fabric. The treated fabric was allowed to sit for 30 minutes covered with aluminum foil to prevent water evaporation. 0.346 g DMTNVM was dissolved in 250 ml of water and the fabric was pulled through this solution, 15 excess solution squeezed out with a padder and allowed to sit covered for 30 minutes. Next, 0.16 mg of DMTMM was added to the mixed dye solution made above and the poly(acrylic acid) treated fabric was pulled through the mixed dye solution, excess solution squeezed out on a padder and the fabric allowed to sit for 30 minutes, then rinsed with water until no further color was seen in the rinse water. 20 This treated fabric had a lavender color. In later testing it was noted that the acridine yellow G did not attach. Example 8 Zinc protoporphyrin IX was converted to an amine derivative by dissolving 50 mg 25 of zinc protoporphyrin IX in 20 ml of dimethyl formamide. To this solution, 10 mg of ethylene diamine was added, followed by 9 mg of N-hydroxy-succinimide, NHS, and 46 mg of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, EDC. The reaction was allowed to proceed for 24 hours. During this time, poly(acrylic acid) of 450,000 g/mol molecular weight was grafted to nylon-6,6 fabric in the form 30 of a bridal veil as follows: a two inch strip of nylon bridal veil was cut. Then 250 mg of poly(acrylic acid) were dissolved in 200 mL of water. Next, 0.05 g of DMTMM was added to the solution and the bridal veil was pulled through the solution and excess solution squeezed out. The fabric was allowed to dry in air over night. The 16 WO 2007/114843 PCT/US2006/043919 treated fabric was then rinsed with water three times and dried. Finally, the treated fabric was immersed in the zinc protoporphyrin IX solution prepared above after adding 0.05 g of DMTMM to the solution. The treated and soaked fabric was then squeezed to remove excess solution, covered and allowed to react for 24 hours. 5 Finally, the fabric was washed extensively with water followed by methanol to remove any ungrafted material. With respect to polymer fabrics to which the singlet oxygen generating dyes can be attached, the following discussion provides additional details. 10 In attaching dyes to polymers, it has been discovered that in general, the surfaces of many polymers have too few reactive groups to attach the singlet oxygen generating dyes. To overcome this difficulty, a surface site mediator or amplifying polymer that contains a large number of reactive sites can be attached. For example, nylon 6,6 15 contains only two reactive groups per molecule, an amino group and a carboxylic acid group. If the dyes are attached directly to the surface of nylon 6,6, there will be too few dye molecules to be effective. However, poly(acrylic acid) can be covalently bonded to the amino ends or poly(ethylene imine) can be attached to the carboxylic acid groups. Both of these polymers contain a reactive group in each repeat unit. 20 Thus, using poly(acrylic acid) and covalently attaching it to the nylon 6,6 surface can increase the number of reactive sites several hundred to several thousand fold. A suitable choice of dyes can then be attached to the surface at much higher levels than without this surface site amplifying polymer. 25 In picking a polymer, it is important to note that in cellulosic polymers, the concentration of reactive groups on the surface is adequate so that the surface site mediator or amplifying polymer is not needed. For each polymer the surface site mediator or amplifying polymer must be chosen to 30 contain reactive groups that are capable of reacting with groups on the surface. Reactive sites commonly found on the surface of fibers include hydroxyl (-OH), carboxylic acid (-COOH), and amino (-NH 2 or -NH-) groups. Other groups may 17 WO 2007/114843 PCT/US2006/043919 also be present or can be added to the surface by means known to those skilled in the art, such a plasma treatment, UV-activation, corona treatment, and etc.) Suitable surface site mediator or amplifying polymers include poly(acrylic acid), 5 poly(ethylene imine), poly(vinyl alcohol), poly(maleic anhydride), poly(ethylene-co maleic anhydride), poly(vinyl phenol), and their copolymers with ethylene, propylene or other materials (known to those skilled in the art). The dyes can be attached to these surface site amplifying polymers through covalent 10 bonding of suitable groups on the dyes to the reactive functional groups in the surface site amplifying polymer. For example, a dye containing an amino group can be covalently bound to poly(acrylic acid) by forming an amide bond between the carboxylic acid groups of poly(acrylic acid) and the amino group(s) of the dye molecule. Azure A is an example of a dye that can be covalently linked to 15 poly(acrylic acid) by reacting the -NH 2 group on Azure A with a -COOH group of the poly(acrylic acid) repeat unit. Other dye-surface site amplifying polymer combinations can also be used, as will be obvious to one skilled in the art. If the dye contains a reactive group, but it cannot react directly with the surface site 20 mediator or amplifying polymer or the polymer surface, a short linker molecule can first be covalently bonded, for example, to the dye followed by covalently bonding the modified dye to the surface site amplifying polymer or the polymer surface. The order of bonding can be reversed, such that the linker molecule can first be attached to the surface site amplifying polymer or the polymer surface followed by covalently 25 linking it to the dye. The short linker molecule should have one or more groups that can be covalently linked to the dye and one or more groups that can be covalently linked to the polymer surface or the surface site amplifying polymer. These groups may be different or they may be the same. The choice of linker molecule reactive groups will be obvious to one skilled in the art. For example, to attach a dye that 30 only has carboxylic acid reactive groups to a carboxylic acid based surface site amplifying polymer, a diamine, such as ethylene diamine, hexamethylene diamine, etc., can first be attached to the dye molecule followed by attachment to the surface site amplifying polymer. 18 WO 2007/114843 PCT/US2006/043919 In accordance with further aspects of the invention, singlet oxygen production is optimized under solar, tungsten lamp, fluorescent light illuminants and ambient light and/or light typically as low as 2500 Lux when multiple dyes are used. In such a 5 case, at least two dyes may be used, and preferably three, each having a spectrum of absorption to generate singlet oxygen different from that of the others. In the case of acridine yellow G, exposure to light as low as 500 Lux served to inactivate at least 99% of viruses exposed to singlet oxygen generated thereby. In 10 one specific and effective application, acridine yellow G, or other dyes of the structure described herein, can be employed with two other dyes which generate singlet oxygen when each additional dye is exposed to light at a different spectrum from that of acridine yellow G and the other dye. 15 Candidate dyes are chosen as those that generate the most singlet oxygen per unit light intensity for specific light sources simulating solar, indoor and fluorescent lighting. The dyes or combinations are attached to a mediator polymer that permit them to be attached to the surface of filter media. 20 In one embodiment, the invention also involves methods for applying the photo active dyes to the surface of air filtration media while maintaining singlet oxygen production efficiency, filtration efficiency, and low pressure drop across the filter. Dye-carrier combinations are optimized as can be understood by one of ordinary 25 skill to correct for any changes in the dyes' activity upon attachment to the carrier. The dye-carrier combinations are attached to the filter media surfaces. The conditions for attachment are optimized to: 1) maximize singlet oxygen generation; and 2) minimize changes in the air filtration performance. 30 The invention results in a real world environment application by resulting in a mask that inactivates influenza virus. 19 WO 2007/114843 PCT/US2006/043919 The inventors herein have developed a less expensive, more robust method of attaching materials to surfaces using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4 methylmorpholinium chloride, DMTMM, other types of amide bond formation or just with heat. Heat is a simple and low cost method of attaching the dyes. The cost 5 of applying these materials has been reduced and the class of dyes has been expanded to include Rose Bengal, Azure A and related dyes. Many singlet oxygen producing dyes can now be attached to the surface of nylon or other materials as obvious to one skilled in the art using the techniques described herein as part of this invention. 10 When the dye contains a carboxylic acid group, it is grafted either to poly(ethylene imine) through the NH group on the imine or by first grafting it to a diamine such as ethylene diamine or 1,6-diaminohexane. When the dye contains a free amino group, it will be grafted directly to poly(acrylic acid). Two approaches are used to attach 15 carboxylic acid groups to amino or imine groups. First, to ensure grafting, 4-(4,6 dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, DMTMM, is used. As an alternative to polyacrylic acid, another approach, which is the preferred embodiment due to reduced chemical usage and reduced cost is to form the amide 20 directly by heating the acid containing and amine containing groups to drive off water. This approach is used to produce billions of pounds of polyamides annually and is a commercially viable route. Recent efforts in the laboratory indicate that the dyes can be readily attached to poly(acrylic acid) using this approach and that poly(acrylic acid) or the dye-modified poly(acrylic acid) can be attached to nylon. 25 Specifically, Azure A is grafted to poly(acrylic acid) by dissolving both in a water solution and adding DMTMM. After stirring for 30 minutes, the unreacted Azure A is removed by dialysis using a Millipore Amicon Ultra 100,000 molecular weight cut-off filtration membrane and a centrifuge. This retains any Azure A that has 30 grafted to 450 kD poly(acrylic acid) and pass any unreacted Azure A. A similar reaction is performed by refluxing an alcoholic Azure A and poly(acrylic acid) solution for 60 minutes and dialyzing to remove unreacted Azure A. 20 WO 2007/114843 PCT/US2006/043919 Since singlet oxygen is required to inactivate viruses in accordance with the invention, it is essential to maximize its production. The amount of singlet oxygen produced depends upon the absorptivity of the dye, the quantum yield of the dye (amount of singlet oxygen produced per photon absorbed), the overlap of the 5 absorption spectrum of the dye and the emission spectrum of the light source, and the intensity of the light source. Other critical factors in choosing suitable dyes include their resistance to degradation via reaction with singlet oxygen, the ease with which the dye can be attached to the surface and its cost. 10 Fortunately, the emission spectra of solar, tungsten, and fluorescent light illuminants are well known In addition, the absorption spectra and quantum yield for singlet oxygen production have been determined for many commercially available dyes. The absorption spectra and singlet oxygen quantum yields are easily measured for other dyes using the test chamber and singlet oxygen analysis procedure, described 15 later herein in this document. In addition, the available reactive sites on many fiber types are known and it is a simple matter to attach the dyes to the surface or to a binder molecule which can then be attached to the surface. The following is a further example of a use of the invention. 20 Madin-Darby canine kidney (MDCK) epithelial cells are cultured in Dulbecco's modified Eagle's medium (DMEM) supplemented with 10% fetal calf serum, 100 U/ml penicillin, and 100 ptg/ml streptomycin. MDCK cells are grown in 75 cm 2 polystyrene cell culture flasks at 37 0 C and 5 % C0 2 . These cells support growth of a 25 wide range of animal viruses including VSV, Vaccinia, adeno and reoviruses, and influenza viruses. Influenza A/WSN/33 virus (HlN1) are propagated in MDCK cells. A/WSN/33 is a common laboratory strain. It replicates in a variety of murine tissues and cultured cells. 2 cm 2 treated or control fabric sections is soaked in a virus suspension of -2 x 108 plaque forming units per ml then transferred to 35 mm cell 30 culture dishes. The dishes containing virus-soaked fabric sections are placed below the desired light source and illuminated for the indicated length of time. Light intensity is measured with a visible light meter. Following illumination, fabric sections are transferred to 15 ml conical polypropylene tubes containing 3 ml of 21 WO 2007/114843 PCT/US2006/043919 serum-free DMEM. The tubes are vortexed for 10-15 seconds to release viruses from the fabric into the culture medium. The virucidal activity is analyzed by serial dilution by factors of 10. The data is 5 reported as Initial number of plaque forming units N Number of plaque forming units after light exposure where N is the "log kill" ratio for this treatment. A log kill ratio of three indicates that 99.9% of the viruses are inactivated by that filter media with the specified exposure. Each measurement is performed ten times and both positive controls and 10 negative controls are used to ensure that the test is valid. The log kill ratios are compared for each of these cases to determine whether adequate protection was obtained using this approach. Adequate protection is defined as a log kill ratio of 2 (99% inactivation) after 30 minutes exposure. 15 Specific filter applications are contemplated as possible for use with influenza as a personal filter. In addition, following are other possible applications of the invention described herein. 1) Filters home HVAC systems 20 office buildings hospitals; and aircraft cabin filters. 2) Masks: 25 military homeland defense NIH "pandemic" international; and retail 30 3) Furniture and furnishings: hospital waiting rooms hospital operating theatres 22 wallpaper chairs day care centers; military uniforms; and 5 aircraft cabin upholstery andi wall cc verings. Having thus described the invention in detail, it wilI be better understood from the appended claims in which it is set form in a!non-limiting manner. 10 In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variati ns sucl as "compri es" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further f atures in various 15 embodiments of the invention. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission tat the publication forms a part of the common general knowledge in the art, in A stralia or any othej country. 20 23 3839070_2 (GHMalters) P79189AU
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Eric was great. Showed up early to ensure he was set up and ready to shoot. I haven't gotten the photos back yet, but the few that I do have look great. Would definitely use him again.May 5, 2019VerifiedeClarke Photography's reply
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I hired Eric for my holiday party in 2017 and already booked him for this year's! He was on time, really nice, took great photos and everyone loved him. Look forward to seeing him again!Aug 24, 2018Verified
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5 Tips on What To Look For When Buying Diamonds For Wedding Rings
A wedding, or an engagement in Nespelem, is one of the most important events in every couple's life. One of the best ways of making the experience memorable is by choosing the right ring to symbolize the love you have for one another. While most couples would like to get the most beautiful ring they can lay their hands on, budgetary restrictions can be a challenge. However, it is possible to find an ideal ring based on your budget.
For anyone looking for precious diamonds for engagement rings and wedding rings in Nespelem, they should consider going about the process carefully. There are various dealers in the market, some of who may sell you fake diamonds. Here are a few useful tips on what to look for when looking for precious diamonds for engagement or wedding rings.
Consider the Diamond Cut
1. Any expert will tell you that the cut is the most important thing to consider when buying diamonds in Nespelem. The main reason behind this is that the cut usually influences the sparkle. A diamond may be clear and feature a high quality color grade, but if the cut is poor, it may still appear dull. The dealer you buy from should be able to cut your diamond in the proper proportions. If your budget can allow it, choose a diamond with the highest cut grade.
Diamond Color
2. Contrary to common belief, lack of color in your diamonds denotes a higher color grade. Some people go for pale yellow diamond, without knowing that it is low quality. To avoid such an experience, ask the diamond dealer to give you grade H or higher. Near colorless diamond ranges from grade G to J, but it may be quite expensive.
Clarity Diamonds can also be chosen based on their clarity levels.
3. This is usually not a very important factor to consider, considering that the precious stones usually come with imperfections, known as inclusions. These tiny imperfections may not be easy to detect, and they may only be seen through a microscope. However, the fewer there are, the higher the clarity grade of your diamonds. If your budget can be stretched further, consider buying grade VS1 grade or higher.
Consider the Diamond's Carat Weight
4. Unlike common belief, carat does not mean the size of the diamond, but its actual weight. Carat and cut must be considered side by side, because no matter the size of the diamond, a poor cut grade can make your precious stones look smaller. Another important fact to keep in mind is that the more the weight of the diamond, the more you will pay for it. Therefore, you should consider going for a less heavy stone with a high grade cut.
Ask for Proof of Certification
5. There is nothing as unfortunate as buying diamonds for your special event only to realize that they are of poor quality, or that they were stolen. To avoid such an eventuality, always ask the dealer in Nespelem to show you the copy of diamond certification.
With these tips, you should be able to make the right choice when buying precious diamonds in Nespelem for you engagement or wedding.
Nespelem How to Buy a Diamond And The 4 Biggest Mistakes When Buying a Diamond
Not all sellers supply ruby grading lab reports (aka diamond top quality records) to their consumers. So my basic advice to you is to maintain your loan in your pocket when handling such jewelry experts.
Just buy a diamond interaction ring if it has the original ruby quality report.
A lab record is an independent assessment of the 4Cs of a loosened diamond as well as consists of an outlined representation of the rock's clearness characteristics and also a visuals representation of the stone's proportions. Having such a report enables you to compare diamonds of different top qualities and also eventually helps you make a more informed purchasing decision.
A retailer may cut corners as well as not give a lab report or a deceitful seller could supply a phony one due to the time, trouble as well as expenditure he'll birth to obtaining a rock rated.
Yeah - there is a rate for grading a ruby (though that expense is ultimately paid by the customer), plus the delivery as well as insurance policy charges for sending out the ruby to the laboratory. As well as allow us not forget the chance cost of a jewelry expert not having the ruby in his store for sale for a couple of weeks while the grading happens.
Nevertheless, a diamond grading report could also not be offered because the prices to obtaining one may affect too greatly on the final price of the ring. For instance, a 0.3 ct ruby ring setting you back $250 claim, could cost around $75 to be graded and have the report number etched on the girdle on the diamond. As you look for that optimal diamond involvement ring for your sweetheart, you'll locate that there is a hodgepodge of labs asserting to offer trustworthy ruby grading records. But I would just place my money on ...
The Premier Ruby Grading Laboratory Information
Yes, all ruby high quality reports are not developed equal. Within the sector, it is a consensus that both top labs are GIA-GTL (Gemological Institute of America's Gem Profession Lab) and the AGS (American Treasure Society Laboratories).
The GCAL (Gem Certification and Assurance Laboratory) likewise supplies highly concerned records or "ruby certificates" as they are referred to by GCAL. The GIA has the best international credibility for self-reliance and also uniformity. Because of their continuous shade as well as quality strictness guidelines, the world's biggest as well as most pricey diamonds have actually been sent out there for rating decades. In 2006, GIA-GTL included a two-dimensional cut grading system for rounded brilliant rubies.
AGS makes use of the most strict cut criteria in the market. It makes use of a three-dimensional light efficiency metric that could grade numerous ruby shapes. As a matter of fact, it is the only cut grading system that is identified by the scientific community.
What is even more, its Ruby High quality Paper makes use of an one-of-a-kind and also exclusive 0 to 10 grading system to review the 4 Cs - a system which is simpler to understand compared to GIA's grading system. Actually, AGS even goes the additional action by equating their 0-10 score range to various other forms of ranking. As an example, the conventional VS1 ruby clearness ranking is a 3 on the AGS Ruby High Quality Document.
Diamond Coverage - The Drawbacks
1. Diamond grading is not standard or regulated and for this reason you may encounter rate 2 labs that utilize looser guidelines to the tier 1 grading labs discussed over. If you get a ruby that has been graded by a tier 2 laboratory, you could end up paying extra for a lesser high quality diamond. So for instance, a diamond rated a "F" in shade at a tier 2 laboratory may obtain a G, H, or lower color score at a much more credible lab. The market also marks down rubies rated by lesser known laboratories by about 15-30% or even more. So either you only purchase a ruby rated by a tier 1 laboratory or you approve that you may be getting a lower quality diamond than what is stated on the record if that ruby is rated by a minimal well-known lab.
2. Several large store have massive agreements with minimal recognized laboratories with "softer" diamond grading standards. A few of these softer labs placed "recommended replacement values" on the laboratory reports - worths which are above what stores plans sell the rubies for. So a salesperson in a store could state to you, "Consider the lot you are getting here. We are selling you this diamond involvement ring for $2500 but the report says that the recommended substitute worth is $4000." Wow - what an offer - NOT! This is why it is better that you rely on just independent rate 1 laboratories.
Likewise bear in mind that credible ruby grading records are not appraisals and don't use evaluation numbers. Diamond evaluations are usually blatantly inflated as well as are not something you'll wish to count on.
3. Ruby records are filled with please notes that specify that absolutely nothing is "licensed" or guaranteed and also that the labs are not accountable for mistakes. As a matter of fact, the GIA offers a please note of types on their site relating to making use of the word "license." The web site states:
"It is incorrect to state that pupils, grads, their services, or particular gems are "certified" by GIA. The Gemological Institute of America does not certify any person or anything. Neither a trainee neither a graduate that has been granted a certificate or diploma, neither a treasure which has been rated or identified by GIA has been accredited by GIA".
So it is feasible that you the customer is left holding the bag should an error in a record is later uncovered. Courts have actually frequently ruled that sellers, not labs, are in charge of such errors. Why? Because the labs suggested ahead of time that their records could not be held responsible.
Luckily, there are a couple ways to offer yourself extra purchaser defense:
A. You can fly to India where jewelry experts offer a lifetime buyback policy to their clients. Too pricey to fly?
B. You could discover one of the 20% people jewelers that sell totally bonded diamonds. These are rubies that are marketed with life time breakage, lifetime trade-in as well as life time buyback policies.
C. Not as great a solution as buying a totally adhered ruby yet you could acquire a diamond that comes with a real "certification" and not a report. "Licensed diamonds do have warranties" albeit for much shorter durations.
Certification Some vendors refer to a "ruby record" as a "qualified ruby" but practically this is not remedy. From a lawful perspective, a ruby record is a just a professional viewpoint though in reality, facets of a diamond grading report are not just viewpoints.
As an example, a ruby's carat (weight) could be properly identified in addition to its cut quality by gauging its optical efficiency or by describing a computer system version. A certification on the various other hand is a declaration of fact - a record for which the issuer approves lawful obligation as well as will certainly make restitution to the consumer for blunders.
Some top diamond grading labs provide both reports and also certificates. AGS offers Ruby High quality Records (non-certified records) as well as Diamond Quality Certificates. Diamond Top quality Certificates are ready specifically for AGS retail jewelers and provides warranties from taking part American Treasure Society participant shops.
GCAL certifies it's ruby grading likewise. Its 100% money-back assurance policy stands for a duration of 2 years from the date on the applicable certification. This policy makes sure the accuracy of the cut, color and clearness qualities and also the carat weight.
A record or certification need to will have a number on it that might or may not be inscribed on a diamond. You will be able to enter that number on the site of the licensing lab to check a record's legitimacy.
Elements Of A Diamond Grading Record Ruby grading reports are constantly developing yet certain component needs to stay the very same. For example, the:
The Record #. This number is given and also recorded in a lab's record and also might or may not be inscribed on a ruby's girdle. You could get in the report number on a grading laboratory's site to check the authenticity of the ruby quality report or to obtain even more information about the ruby. Shape & Aspect Design: This is the summary and also the reducing style made use of for the element arrangement. There are 3 standard element designs - "brilliant cut, action cut as well as blended cutting design" and 12 standard shapes that include notables such as rounded fantastic and princess cut" diamonds.
Dimensions: This refers to dimension (not weight) of a ruby. Dimension includes measurements such as length, size, weight and also size. A dimension is normally noted to the hundredth of a millimeter. Measurements play a substantial function in just how a diamond glows.
Carat Weight: The weight of a ruby is measured to the hundredth of a carat weight and also some even give such step to the thousandth of a carat (1.123 ct.). Carat weight is one of the most unbiased and the easiest to comprehend of the 4Cs due to the fact that all one has to do is weight the stone. Shade Grade: This informs you the degree of color absence in the ruby. The less shade the higher the grade.
Diamonds are usually graded from D-Z; the closer to "D" the whiter the diamond. You should never ever see diamond color variety such as (G-H, I-J-K, and more) on a ruby record. You need to just see color arrays on assessments for stones that are mounted.
Quality Quality: Basically every ruby has interior blemishes called additions as well as exterior blemishes called blemishes. A ruby is graded according to the dimension, type, location and quantity of these problems.
Clearness qualities range from Perfect (FL) - Consisted Of. Labs utilize a pair specialists to grade the clarity of a diamond in order to think of a more accurate reading.
Cut Grade: A lot more current ruby reports consist of a cut grade for standard round dazzling diamonds. Cut considers the sparkle, fire and also scintillation of the diamond. Cut quality varies from Superb - Poor.
Other elements you could find on a diamond report consist of the polish, symmetry, fluorescence and also proportion. Equipped with this information, you are much better able to make an evaluation of the high quality of diamond that is mounted in an involvement ring.
Fake Or Real Diamond And Also Is This Right For You
Diamonds are naturally readily available in a very large array of colors. Most individuals find out about colorless rubies and also GIA's shade grading system that is made use of to identify a diamond's body color ... you know D, E, F, and so on. This color grading system is just utilized to identify one of the most common diamond body shade of yellow nevertheless anytime a ruby is found in another shade like pink, blue, green, etc.; then this ruby is described as a "" fancy ruby"".
All-natural Fancy rubies can be extremely pricey and also lot of times extra costly compared to a comparable size anemic ruby. A really great instance of a Fancy ruby is the infamous 45.52 carat weight elegant deep blue ruby, the Hope Ruby, which is on screen in the Smithsonian Natural Background Museum in Washington, DC.
A color improved diamond is a 100% all-natural diamond that has had its color altered. As well as best of all, color boosted rubies come in an extremely large option of colors at very affordable rates!
A little bit of history- For many, years it has actually been popular that a ruby's color can be "" enhanced"" by putting a little tinted substance on the surface area of a ruby and also just like magic ... a ruby that had a visible yellowish color would change to a more eye-catching near colorless diamond. However, this sort of color improved diamond can alter back to its original body color if this tinted material was accidentally eliminated. In even more recent years, the modern technology of shade enhanced diamonds has gone incredibly high technology. It is currently possible to entirely alter the shade of a ruby! These processes are taken into consideration permanent because it does continue to be secure when subjected to daily normal conditions. The color will certainly not fade if revealed to sunshine or be cleaned off by harsh chemicals.
How is it done? The desired result of any one of these treatments is to have a more marketable diamond. A much less valuable diamond would certainly be a ruby that has a low body color or sometimes a reduced clearness. The shade boosted diamond therapy companies understand if they begin with a particular sort of ruby as well as procedure it for a certain quantity of time that they need to finish up with a specific shade but it does not always work that way. This is a science that does call for some art in their processes ... the only process that provides regular outcomes is the finish process.
The three processes are as adheres to- Refine # 1- HPHT Shade Improved Diamonds- High Stress/ Heat (HPHT) treatment can boost the color of specific kinds of brownish diamonds and hence boost their worth. General Electric has established a procedure that basically is a mechanical simulation of a ruby's development in nature. The color enhanced ruby will be warmed up to a very high temperature under an extremely high, supported stress. Faults in the crystal structure are after that rearranged causing a modification of the ruby's shade. Because the problems of HPHT are very much like diamond's initial development, just a well geared up lab will certainly be able to positively recognize this type of shade improved diamond. HPHT was first made use of to turn yellow-colored rubies into even more marketable fancy colored boosted rubies, and now it is likewise made use of to transform some unpopular brownish rubies into better colorless colored boosted diamonds.
Process # 2- Irradiated Color Enhanced Diamonds- OK ... do not begin getting all thrilled due to the fact that you saw words irradiated! This is a 100% secure process that is very comparable to just what is used to protect food by revealing it to a stream of Gamma rays. The color enhanced diamond process is carried out in numerous various ways however the results are all the very same. You begin with a reduced color (P, Q, R, and so on) 100% all-natural diamond that has actually already been cut and polished, then it is revealed to a stream of quick electrons. During this component of the procedure the ruby will resort to a very dark shade because a few of the atoms in the ruby's crystal structure have actually currently been disjointed and this in turn has actually impacted the method light passes with the diamond. Next the diamond experiences a controlled heating (annealing) process, this permits several of those atoms to move (partially fixed) in order to obtain a desired color.
Refine # 3- Layered Shade Improved Diamonds- The layer on polished diamonds describes a thin artificial layer that modifies the color of the ruby. The coating can either be of the preferred shade or could trigger a tinted interference-effect. However occasionally this procedure is done to deceive a customer. It is a fairly easy process to carry out, it has actually been around for several years (although the finishings products are a lot better currently), and it does not call for a great deal of costly high technology devices. Just recently, I have actually seen some pink layered rubies on the market, they are really attractive ... and of training course you would certainly have to buy them understanding that they have been covered and also follow your jeweler's guidelines concerning possessing as well as taking care of these color boosted rubies. The finishing can be put on the whole of a diamond's surface area, just all-time low of the ruby, or to a slim zone near the band. A well-applied finish can alter the shade by several color grade. Some finishes can be eliminated via steaming in acid, strong cleansing solutions, or even house chemicals. Often dots or larger areas of purple or blue ink are repainted on the diamond to assist neutralize a yellow-colored color. The diamond's setting will normally cover the dots, so they are challenging to see in an installed rock.
So, is a shade enhanced ruby right for you? Maybe ... all-natural elegant color rubies can be gorgeous however they are expensive! Shade enhanced rubies are budget-friendly and also allow several individuals to possess a brilliantly tinted diamond. Ask your regional jeweler if they have any kind of Fancy diamonds ... either all-natural or shade boosted diamonds. It is always intriguing, and fun, to check out something different!
Under normal wear the irradiated as well as HPHT color improved rubies will certainly have no issues of the color fading away. The only factor to consider will certainly be when you require to have any kind of kind of service done on the piece of jewelry. If this kind of shade improved diamond is exposed to too much quantities of heat it could impact the shade. The jewelry expert will certainly require to understand that the ruby is a shade improved diamond before any kind of work is done and afterwards the jewelry expert will have the ability to select the best strategy. Shade enhanced rubies are now likewise utilized as the tiny accent rubies around a bigger colorless ruby. There are numerous exciting items of fashion jewelry offered with small blue, yellow, black, or environment-friendly shade boosted diamonds.
Currently that you find out about shade enhanced rubies and a person attempts to market you on exactly what they call an all-natural elegant colored ruby but it goes to an extremely bargain cost ... you will know that something just does not appear appropriate about the offer. A record from a highly regarded grading laboratory must go along with natural Fancy colored rubies that are marketed as natural. If you take care of a reliable business and also you have been comforted concerning what you are getting, after that you will reduce the possibility of something bad taking place to you. Similar to any type of situation entailing a costly purchase of something that few individuals are experienceded in, education should be a vital part of your plan. This is also much more essential if you plan to acquire a color improved diamond. Bud Boland has actually remained in the fashion jewelry organisation for 40 years as well as has done everything from watchmaking, diamond setting, fashion jewelry production, as well as has actually been a Gemologist for virtually 35 years. He is a Graduate Gemologist from GIA (Gemological Institute of The U.S.A.), which is additionally the area where he was a Trainer. He has taught regarding diamonds to thousands of trainees from throughout the globe


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Meet the fearless female professor who helped bring down Elizabeth Holmes
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Frances Burney had her breast removed without anaesthetic in 1811. Here, she describes the experience
Thousands of women with previously untreatable breast cancer will have access
The new directive will start in 2019
Doctors are finally being warned to take period pain seriously
New research argues that men should be sharing more responsibility for avoiding pregnancy.
The devices are supposed to help women to recover from side-effects of childbirth.
"I'm in the family way again, and I'm nearly crazy..."
"Being a doctor isn't a profession, it's a way of life"


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"Her skin was pulled so tightly that her eyelids had flipped inside out. We were informed her limbs could suddenly detach on their own. Every day, we faced a new challenge."
'I rushed to the hospital. 'I've never seen anything like this,' the surgeon said. Our pregnancy checkup had gone well. There was never a reason to believe something was wrong. Our excitement turned to disbelief.'
'His skull looked as thin as a piece of paper. We were given the option to terminate at 7 months pregnant. He's not dead yet.'
"The next day I got the call. 'Jessica, can you come into the doctor's office tonight?' I was just heading out the door for work, but she said, 'Jessica, you need to come in now please'."
'Her skin hardened within seconds. After hardening, it began to split. Behind the curtain, I sensed their frantic panic. My husband's silence scared me. He kept saying, 'It's bad.'
"He told me, 'Jennie, I looked in her eyes, and she has the most beautiful soul.' Broken is the only way to describe the feeling as they placed her in my arms. They had never seen anything like this. She was fine; everything was perfect, and then it wasn't — just like that."
'Honey, there is something wrong with his leg.' I was exhausted, delirious, and just wanted to hold my baby, but I will never forget my response. 'I'm sure it's just a bruise.'
"In my mind he was the most beautiful thing I had ever laid my eyes on. My rainbow baby. But, would he be OK? He baffled them all."
'It is not my job to be a decoration at the beach': Strangers unite to write 'hurtful words' on each other to 'wash away' negativity, celebrate their 'bikini bodies'
"We found there is a common bond, among every single one of us, regardless of body type, that we have been shamed by others, and it was time to wash those words away."
'Our baby had a head full of hair — WHITE AS SNOW': Mom's shocked reaction to albino newborn
"My daughter told me her sister was a snow fairy, and informed me she was related to Elsa. I should have known children see no differences."
'My dog was so persistent': Rescue dog detects cancer on owner's nose, saves her life
"She senses when I'm upset or stressed; I had no idea she'd be able to detect that I had cancer lurking underneath my skin."
How to make the DIY dry winter skin remedy blowing up the Internet
Get this woman's super easy dry winter skin remedy!


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Astronomers using ESA's Herschel and NASA's Spitzer space telescopes have detected surprisingly rapid changes in the brightness of embryonic stars within the well-known Orion Nebula. Images from Herschel's far-infrared instrument and two of Spitzer's instruments working at shorter wavelengths give .
Alien skulls or Elongated skulls are found all over the world. Egypt, Central america, South-america and more. Were did these strange skulls came from? Dozens of such elongated skulls have been found in many other places of the world, primarily in South and Central America in .
President Eisenhower had three secret meetings with aliens, former Pentagon consultant claims One of the strangest stories in which the American president has been linked to has to be the story of President Eisenhower, who was believed to have actually communicated .


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But not nearly in the numbers that you will find in Pikeville! : )
I spent two days in pikeville, thanks to being in a wedding. I can say that I saw at least ONE if not more of everything they say was portrayed in the article, in that two day period.
There is nothing wrong with the Rebel Flag. I have one in my garage and the US Flag on my mailbox.
So, there is nothing wrong with having an old pickup and a few wymins in the back.
Spares, doncha know........