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Calcium phosphate compositions that are particularly useful and unique as orthopedic and dental cements and remineralizers, as well as methods and kits for their use, and the resulting products are disclosed. The compositions comprise tetracalcium phosphate which has been prepared from a mixture with a calcium to phosphorous ratio of less than 2, or prepared and maintained under substantially anhydrous conditions prior to use or, preferably, both. The novel compositions are converted substantially to hydroxyapatite upon setting, are substantially gradually resorbable and replaced by bone when implanted in contact with living bony tissue, and offer distinct advantages in terms of cement strength, setting time and reliability and other properties.
1. An improved method for preparing a tetracalcium phosphate based calcium phosphate-containing composition comprising combining tetracalcium phosphate and at least one other sparingly soluble calcium phosphate, wherein the improvement comprises employing tetracalcium phosphate which is substantially free of calcium oxide.
2. An improved method for preparing a tetracalcium phosphate based calcium phosphate-containing composition comprising combining tetracalcium phosphate and at least one other sparingly soluble calcium phosphate compound wherein the improvement comprises employing tetracalcium phosphate which is substantially free of surface hydroxyapatite prior to use.
This invention was made in the course of research partially supported by a government grant from the National Institute of Dental Research (Grant No. DE 05030). The U.S. government has certain rights in the invention.
This is a continuation of application Ser. No. 08/030,709, filed Mar. 12, 1993, pending.
1. Field of the Invention
This invention relates to calcium phosphate compositions, including cements, pastes and slurries, and to the methods for making and using them. In particular, the invention relates to hydroxyapatite forming cements, pastes and slurries prepared from a set of precursors which includes tetracalcium phosphate.
2. Description of Related Art
It has been known for some time that hydroxyapatite materials have the basic properties of human bones and teeth. A considerable amount of research has been directed to the remineralization of incipient dental lesions by deposition of hydroxyapatite, Ca5 (PO4)3 OH, on such lesions, so that the hydroxyapatite is incorporated into the dental structure at the point of lesion.
Remineralization of tooth enamel has been carried out experimentally both in vivo and in vitro. These studies have concentrated on the remineralizing properties of saliva and synthetic solutions supersaturated with respect to hydroxyapatite. Two articles that give a good overview of this research are Briner et al., "Significance of Enamel Remineralization", J. Dent. Res. 53:239-243 (1974); and "Silverstone", "Remineralization Phenomena", Caries Res. 11 (Supp. 1): 59-84 (1977). Additional experimental work in the areas of remineralization of calcium phosphate biomaterials may be found in Gelhard et al, "Rehardening of Artificial Enamel Lesions in Vivo", Caries Res. 13: 80-83 (1979); Hiatt et al., "Root Preparation I. Obduration of Dentinal Tubules in Treatment of Root Hypersensitivity", J. Periodontal. 43: 373-380 (1972); LeGeros et al. "Apatite Calcium Phosphates: Possible Dental Restorative Materials", IADR Abstract No. 1482 (1982); Pickel et al. "The Effect of a Chewing Gum Containing Dicalcium Phosphate on Salivary Calcium and Phosphate", Ala. J. Med. Sci. 2: 286-287 (1965); Zimmerman et al., "The Effect of Remineralization Fluids on Carious Lesions in Vitro", IADR Abstract No. 282 (1979): and U.S. Pat. Nos. 3,679,360 (Rubin) and 4,097,935 (Jarcho).
Generally, the supersaturated solutions or slurring used for remineralization experiments have been prepared from a single form of calcium phosphate. However, these solutions or slurring have been unsatisfactory for a variety of reasons.
In the area of dental cements, the prior art shows an array of compounds. Some cements, however, irritate the pulp and are unsuitable for applications where the cement must come in contact with exposed pulp. Guide to Dental Materials and Devices, 7th Ed. (ADA 1974) p. 49. One solution to this problem is a cement made of materials similar in composition to tooth and bone mineral, since this would not irritate the living tissue.
The use of β-Ca3 (PO4)2 was suggested for pulp capping in Driskell et al., "Development of Ceramic and Ceramic Composite Devices for Maxillofacial Application", J. Biomed. Mat. Res. 6: 345-361 (1972); and the use of Ca4 (PO4)2 O was suggested by Brown and Chow in IADR Abstract No. 120, J. Dent. Res. 54: 74 (1975), as a possible pulp capping agent. As described in the latter, Ca4 (PO4)2 O hydrolyzes to hydroxyapatite.
Such single calcium phosphate cements are incapable of setting to a hard consistency, however, and suffer from the same drawbacks as single calcium phosphate remineralizers. They cannot maintain a relatively constant pH and do not have sufficient remineralization capacity. Though U.S. Pat. No. 3,913,229 (Driskell et al.) discloses putty-like pastes containing α-Ca3 (PO4)2, β-Ca3 (PO4)2, CaHPO4 and mixtures thereof as pulp capping, root canal, and tooth replanting materials, it is believed that none of these pastes harden into cements. Furthermore, no remineralization properties are disclosed and it is believed that none of these pastes are capable of any substantial remineralization.
Experience with calcium-based implants for the replacement of skeletal tissue has also existed for many years. Most of these implants have been in the form of prefabricated, sintered hydroxyapatite in either granule or block forms. These preparations have several drawbacks, including a limited ability to conform to skeletal defects, particularly in the case of blocks; inadequate structural integrity of granules (which do not bond together), and difficulty in modeling the implant to the shape of missing skeletal tissue with both blocks and granules. The block form of hydroxyapatite provides structural support, but among other complications, must be held in place by mechanical means, which greatly limits its use and its cosmetic results; and it is very difficult to saw a shape such that it fits the patient's individual defect. The granular form produces cosmetically better results, but has a very limited structural stability and is difficult to contain during and after a surgical procedure. In general, all of these products are ceramics, produced by high temperature sintering, and are not individually crystalline, but rather have their crystal boundaries fused together. These ceramic-type materials are in general functionally biologically non-absorbable (having an absorption rate generally not exceeding on the order of 1% per year).
A porous, non-resorbable material based on coral allows intergrowth with bone, but ultimately becomes only approximately 20% bone with the remaining 80% subsisting as scar tissue. HA RESORB made by Osteogen is a form of absorbable hydroxyapatite, but is not a cement. It is granular and not adhesive. HA RESORB is loosely rather than adhesively packed into place. For large uses, it is replaced by bone too quickly. In the dental materials market, HAPSET is a composition of calcium phosphate granules and cementable plaster of Paris (calcium sulfate). This material is not truly a hydroxyapatite and contains too much calcium sulfate for most biological uses. The calcium sulfate component of such a composition is resorbable, but not the calcium phosphate granules.
In sum, the commercially available hydroxyapatite materials are in general not resorbable with accompanying replacement by bone, and are not self-setting (self-hardening) cements.
The patent literature, does, however, describe at least one class of calcium phosphate compositions which are precursors for the formation of hydroxyapatite, and which as slurries, offer good remineralization potential; and, as cements, are biologically compatible, self-setting (self-hardening) and substantially resorbable (biodegradable), with bone replacement, when implanted in contact with living bone tissue. See U.S. Pat. Nos. Re. 33,221 and Re. 33,161 to Brown and Chow, which teach preparation of calcium phosphate remineralization compositions and of a finely crystalline, non-ceramic, gradually resorbable hydroxyapatite cement based on the same calcium phosphate composition. Somewhat similar, and in certain instances potentially identical products are described in U.S. Pat. Nos. 5,053,212, 4,880,610, 5,129,905, 5,047,031, and 5,034,059 to Constantz and others, although the use of non-traditional chemical terminology in the latter patents makes interpretation of them and comparison of them with the prior work of Brown and Chow difficult.
The major components of the calcium phosphate remineralizing slurries, pastes and cements taught in U.S. Pat. Nos. Re. 33,271 and Re. 33,161 are preferably tetracalcium phosphate (Ca4 (PO4)2 O), and at least one other sparingly soluble calcium phosphate, preferably dicalcium phosphate anhydrous (CaHPO4), or dicalcium phosphate dihydrate (CaHPO4 •2H2 O). These react in an aqueous environment to form hydroxyapatite, the principal mineral in teeth and bones, as the final product. Because of the apatitic nature of the set cement, it is highly compatible with soft and hard tissues. This material, if applied intraoperatively as a paste, subsequently sets to a structurally stable implant composed of microporous hydroxyapatite.
The materials of Brown and Chow U.S. Pat. Nos. Re. 33,221 and Re. 33,161, while highly useful, were characterized by some variation in reproducibility of hardening and generally only moderate mechanical strength for the set hydroxyapatite. Applicants have discovered that unique steps in the preparation of the tetracalcium phosphate reactant employed in the calcium phosphate composition result in important improvements in the resulting hydroxyapatite. In particular, applicants have discovered that the use of a tetracalcium phosphate precursor which has a calcium to phosphate ratio less than 2 results in a cement which sets more reliably and more quickly to provide a superior product. Applicants have also discovered that calcium phosphate cements with substantially improved setting times and mechanical strengths are obtained when tetracalcium phosphate is prepared under anhydrous conditions. The resulting cements set reliably with concomitant strength attainment. The setting rate can be adjusted for various end uses, and may be quite rapid if desired. The inventive hydroxyapatite cement is both biocompatible and resorbable (biodegradable) with bone replacement when in contact with living bone.
The invention includes a calcium phosphate composition, which self-hardens substantially to hydroxyapatite at ambient temperature when in contact with an aqueous medium, comprising tetracalcium phosphate and at least one other sparingly soluble calcium phosphate compound, wherein the tetracalcium phosphate is prepared from a starting mixture of one or more sources of calcium, phosphorous and oxygen which mixture has a calcium to phosphorous ratio of less than 2. The invention further includes a calcium phosphate composition, which self-hardens substantially to hydroxyapatite at ambient temperature when in contact with an aqueous medium, comprising tetracalcium phosphate and at least one other sparingly soluble calcium phosphate compound, wherein the tetracalcium phosphate is prepared and maintained under substantially anhydrous conditions prior to its contact with the aqueous medium in combination with the sparingly soluble calcium phosphate compound. Alternatively, the inventive calcium phosphate cement's tetracalcium phosphate component may have both these characteristics. The invention includes formulations for increasing the remineralization potential of saliva, and dental restoratives employing the new tetracalcium phosphate-containing compositions.
The invention also includes an improved method for preparing a self-hardening calcium phosphate cement comprising combining tetracalcium phosphate and at least one other sparingly soluble calcium phosphate, in which the synthesis mixture for preparation of the tetracalcium phosphate component has a calcium to phosphate ratio of less than 2. Alternatively, or in combination, the invention includes a significantly improved method for preparing a self-hardening calcium phosphate cement comprising combining tetracalcium phosphate and at least one other sparingly soluble calcium phosphate in which the tetracalcium phosphate precursor is prepared and stored under anhydrous conditions. The invention further contemplates the improved calcium phosphate cements prepared by this method, the cement component(s) provided to the user in a pre-manufactured kit or delivery device, the methods of using the improved cement, and the biological implants made from the cement. A self-hardening industrial cement is also contemplated.
The techniques previously available for repair of cranio- and maxillofacial defects, periodontal defects, bone fractures and other dental and orthopedic defects which could not be successfully self-healed relied heavily on the use of metallic and ceramic inserts and prostheses which might remain indefinitely as foreign objects in the body of a human or veterinary patient. As such, these prior art techniques suffered from a host of related problems, including possible rejection, sites for infection, structural failure, injury to neighboring tissue and the like. Metals are difficult to shape and are hampered by problems such as infection and corrosion. Polymers such as silicone, PROPLAST, or methylmethacrylate are encapsulated by scar tissue resulting in significant rates of implant infection and/or extrusion. Biologic materials, such as autogenous bone grafts, may cause donor site morbidity, may suffer from significant post-implantation resorption, and are difficult to accurately conform to skeletal defects. U.S. Pat. Nos. Re. 33,221 and Re. 33,161 offer the alternative of a hydroxyapatite-forming calcium phosphate cement which is biocompatible and which when implanted in contact with living bone, is largely if not completely replaced by new bone formation, with no significant loss in the volume or integrity of the tissue that receives the implant. The above-cited patents to Brown and Chow teach the preparation of such bioresorbable cements preferably from combinations of tetracalcium phosphate (Ca4 (PO4)2 O) and another sparingly soluble calcium phosphate compound, preferably dicalcium phosphate or dicalcium phosphate dihydrate.
The inventive slurries, pastes and cements described and claimed herein are characterized by many important advantages as compared with traditional hydroxyapatite materials. While the inventive materials are of the same general class as those of Brown and Chow, cited above, and maintains the latter's advantages, they also contributes additional unexpected advantages.
The tetracalcium phosphate prepared and maintained under anhydrous conditions is not contaminated at the crystal surfaces by the less soluble reaction products of tetracalcium phosphate and moisture. The tetracalcium phosphate prepared and maintained under anhydrous conditions is thus believed to be more readily soluble than ordinary tetracalcium phosphate, promoting the quicker release of calcium and phosphate moieties in slurry applications.
With respect to cement applications, the hydroxyapatite cement described and claimed herein sets more quickly, reliably and reproducibly. If other factors (e.g., composition of the liquid phase, powder to liquid ratio, temperature and powder particle size) are held constant at typical values, the inventive cement is reliably fast-setting; in the presence of water or a dilute aqueous acid or base solution, it will set reproducibly in about 15-30 minutes, typically about 20 minutes, and will fully convert (precipitate) to a solid mass of hydroxyapatite in situ within 4-6 hours.
The novel cement is also characterized by significantly improved mechanical strength properties. While the inventive hydroxyapatite cement, without augmentation, may not have sufficient shear-strength resistance to function in the reconstruction of stress-bearing bones, the cement is sufficiently structurally stable for reconstruction and augmentation of relatively non-stress-bearing bony tissue.
Additional advantageous attributes of the inventive cement include the following:
The cement is easy to use. It can be mixed with water, blood, saline, dilute phosphoric acid, or other agents to provide malleability and create a paste or putty. The liquid employed may be only that liquid present at the site where the cement is to be applied, such as blood or saliva. The cement can then be easily modeled to accurately reconstruct bony cavities and missing bone and to recreate contour defects of relatively non-stress bearing skeletal bone.
The cement or paste consistency enables the hydroxyapatite to conform exactly to the contours of the defect. The cement can be applied to the defect, e.g., with a spatula, can be molded and sculpted, and will hold its shape satisfactorily until set.
The inventive cement sets at ambient temperature, e.g., room or body temperature, unlike the ceramic-type calcium phosphate cements which must be sintered at high temperature in a process that fuses individual hydroxyapatite crystals to each other. The cement setting reaction for the inventive material is isothermic (negligible heat is generated) and thus does not result in heat-generated necrosis of any of the neighboring tissue.
The inventive cement can be easily sculpted in vivo (intraoperatively) even after setting. When applied to clean, non-infected bone, the cement adheres to the bone, thereby greatly increasing its possible applications. In general, the cement can be adapted to many applications.
The instant cement represents a highly biocompatible tissue substitute precursor or synthetic implant material for skeletal reconstruction. This biocompatibility stems from the fact that calcium phosphate exists in bone in the form of hydroxyapatite, and it is therefore a chemically natural material. Basically, the inventive cement is regarded by the body as a native material; it triggers no significant or sustained inflammatory response, and no foreign body giant cell reaction.
The absence of fibrous encapsulation and minimal inflammation compare favorably with what is seen with polymer implants such as methylmethacrylate or PROPLAST, and aid in minimizing the potential for infection and implant loss. The inventive cement is non-toxic and non-carcinogenic (non-mutagenic).
Finally, the inventive cement can undergo gradual biointegration. When in contact with viable bone or periosteum, although there is no significant change in implant shape or volume over time, the cement is gradually replaced over the course of weeks and months, at least in part, with osseous tissue, on an approximately 1:1 basis as the implant is resorbed. The cement actually promotes the growth of living bone into the implant, and this osteointegration of the cement with the surrounding bone with variable replacement of the implant by living bone over time results in permanent fusion and further structural stability. The cement is thus remodelled gradually in a manner that resembles the remodelling of living bone. The finely crystalline microporous structure of the implants, which facilitates osteoblast penetration, also permits ion passage, but prevents bacteria from permeating the implant.
FIG. 1 is a graph of the mean diametral tensile strength of calcium phosphate cement specimens prepared using, as the tetracalcium phosphate component, tetracalcium phosphate that had been exposed to 100% humidity air for different periods of time.
FIG. 2 shows the x-ray diffraction spectra of tetracalcium phosphate exposed to 100% humidity for different periods of time, illustrating the growth in the hydroxyapatite spectral shoulder with increasing moisture exposure.
FIG. 3 is the x-ray diffraction spectrum of tetracalcium phosphate prior to grinding and after grinding in 95% ethanol for 20 hours. It illustrates the (undesirable) premature formation of hydroxyapatite.
The complete disclosures of U.S. Pat. Nos. Re. 33,221 and Re. 33,161 are expressly incorporated herein by reference.
The inventive hydroxyapatite cement is an improvement on the self-setting cement of calcium phosphate compounds developed by Brown and Chow. The preferred major components of the calcium phosphate cement of Brown and Chow are tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA) or dicalcium phosphate dihydrate (DCPD). These react in an aqueous environment to form hydroxyapatite (OHAp), the principal mineral component of teeth and bones, as the final product:
Ca4 (PO4)2 +CaHPO4 (or CaHPO4 •2H2 O)→Ca5 (PO4)3 OH
The results from extensive in vitro and in vivo studies suggest that the usefulness of calcium phosphate cement can be further advanced if the following two areas of the cement properties are improved: (1) shorter and more consistent setting times, and (2) greater mechanical strengths.
Described in the following are novel procedures for preparing tetracalcium phosphate and resulting self-setting calcium phosphate cements with greatly improved properties. Aspects of the invention include (1) the calcium (Ca) to phosphate (PO4 ▪ or P) molar ratio in the prepared tetracalcium phosphate should be below 2, and/or (2) the tetracalcium phosphate is kept under a substantially anhydrous environment during its synthesis, quenching, particle size reduction process, and storage.
If the prepared tetracalcium phosphate has a molar Ca/P ratio above 2, calcium oxide is believed to be present in the material as an impurity phase. When such a tetracalcium phosphate sample is used in the cement, the rapid dissolution of the CaO causes the pH of the cement slurry to rise substantially above pH 8.5 (but below 12), which impedes the setting reaction.
It has also been found that tetracalcium phosphate is extremely reactive to water. Thus, when exposed to air, tetracalcium phosphate has been found to react with the moisture present in the air to form a small amount of hydroxyapatite (OHAp) and calcium hydroxide or calcium oxide. It has been discovered that these products coat the surfaces of the tetracalcium phosphate crystals and cause the tetracalcium phosphate particles to become significantly less reactive when used in the cement system. By maintaining tetracalcium phosphate in an anhydrous environment, the undesirable surface contamination by the aforementioned reaction products is minimized. Self-setting calcium phosphate cements with substantially improved setting times and mechanical strengths were obtained when tetracalcium phosphate prepared under anhydrous conditions was used.
The undesirable reaction of tetracalcium phosphate with moisture is irreversible at later stages in its preparation so that drying the moisture-exposed tetracalcium phosphate to remove the water would not suffice to reclaim the properties of uncontaminated tetracalcium phosphate.
Tetracalcium phosphate has the formula Ca4 (PO4)2 O, and a theoretical ideal molar Ca/P ratio of 2.0. Its traditional mode of preparation is illustrated in the following equation:
2 CaHPO4 +2 CaCO3 →Ca4 (PO4)2 O+H2 O↑+2 CO2 ↑ (1)
It is thermodynamically stable only at temperatures above approximately 1400° C.
The inventive preparation of tetracalcium phosphate powder for cement use is illustrated by the following steps:
Preparation of tetracalcium phosphate in a furnace:
To prepare an embodiment of the inventive tetracalcium phosphate one first prepares a homogenous mixture that has a Ca/P ratio of less than 2, heats the mixture to 1400° C. or above, and then maintains the sample at that temperature for a sufficiently long period of time, for example 6 hours, to assure as complete conversion as possible of the starting mixture to tetracalcium phosphate. An example of the starting mixture would consist of 2 moles of CaHPO4 (272 grams) and 1.8 moles of CaCO3 (180 grams). The excess H2 O and CO2 are expelled in the heating process.
One may also use any other types of calcium and phosphate containing compounds to prepare mixtures with a molar Ca/P ratio of less than 2 provided that the non-calcium and non-phosphate components in the mixture can be expelled by evaporation during the firing with or without an accompanying oxidation reaction. For example, the following reactions may be employed with appropriate adjustment of the molar ratios:
2 CaHPO4 +2 CaO→Ca4 (PO4)2 O+H2 O↑(2)
Ca2 P2 O7 +2 CaO→Ca4 (PO4)2 O(3)
Ca3 (PO4)2 +Ca(OH)2 →Ca4 (PO4)2 O+H2 O↑ (4)
4 CaO+2 (NH4)3 PO4 →Ca4 (PO4)2 O+6 NH3 ↑+3 H2 O↑ (5)
2 CaHPO4 +2 Ca(CH3 CO2)2 +4 O2 →Ca4 (PO4)2 O+7 H2 O↑+4 CO2 ↑ (6)
The preparation of the mixture for firing is the only step in the tetracalcium phosphate synthesis in which the presence of water is not a concern. This is because the tetracalcium phosphate is formed only after the firing process.
If the Ca/P molar ratio of the homogenous mixture prepared for firing is above 2, calcium oxide will be present as an impurity phase in the product. Thus, in the reaction represented by equation (1), if 2 moles (272 grams) of CaHPO4 is combined with 2.2 moles (220 grams) of CaCO3, the molar Ca/P ratio will be 2.1, and the reaction in the furnace will be:
2 CaHPO4 +2.2 CaCO3 →Ca4 (PO4)2 O+0.2 CaO+H2 O↑+2.2 CO2 ↑ (7)
The presence of CaO as an impurity in the prepared tetracalcium phosphate is undesirable because during the cement setting, rapid dissolution of CaO raises the slurry pH to approximately 10 to 12, and this greatly impedes the setting reaction to the point that the cement often fails to harden.
While it is essential that Ca/P ratios of greater 2 should be avoided, a mixture with a ratio of lower than 2 is permissible, as far as the cement setting reaction is concerned. This is because in such a case, the reaction impurity by-product will be hydroxyapatite. It is important to note that when hydroxyapatite is formed during the firing process, it is homogeneously dispersed in the prepared tetracalcium phosphate as a phase impurity, and the reactivity of tetracalcium phosphate is not significantly affected. This is in great contrast to the hydroxyapatite coatings that form on the tetracalcium phosphate crystals as a result of reaction with moisture. In this latter case, the hydroxyapatite is highly detrimental to the reactivity of tetracalcium phosphate. Equation (8) given below illustrates the hydroxyapatite as a by-product when a mixture with a Ca/P ratio of 1.9 is fired:
2 CaHPO4 +1.8 CaCO3 →0.7 Ca4 (PO4)2 O+0.2 Ca5 (PO4)3 OH+H2 O↑+1.8 CO2 ↑(8)
A Ca/P ratio of 2 precisely is to be avoided because the inherent error in measurement of the reactants makes actual preparation of a sample with Ca/P ratio greater than 2 a statistical probability in a number of instances, and because cements prepared from tetracalcium phosphate with Ca/P ratio less than 2 have been found to have greater mechanical strength than those with a ratio of 2, as illustrated in the following table:
TABLE I______________________________________Effect of the Ca/P Ratio of TTCP on Diametral TensileStrength (DTS) of Calcium Phosphate Cement______________________________________Ca/P Ratio 2.0 1.96 1.90of TTCPDTS (MPa) 8.34 ± 0.17 8.06 ± 1.64 10.38 ± 0.44Mean ± s.d.(n = 3)______________________________________
To prepare the calcium phosphate cement, tetracalcium phosphate and dicalcium phosphate anhydrous were combined at a molar ratio of 1:1, and mixed with 25 mmol/L phosphoric acid at a powder to liquid weight ratio of 4.0 at ambient temperature.
Diametral tensile strength was measured as follows:
DTS measurement: 0.3 gram of calcium phosphate cement powder was mixed with 0.075 mL of liquid (powder/liquid=4), spatulated on a glass slab for 30 sec, and placed in a stainless steel mold (6 mm d×3 mm h). The top and bottom surfaces of the mold were tightly covered with glass plates and the mold was placed in a 100% humidity box kept at 37° for 4 hours. The sample was removed from the mold and placed in a small amount of water for 20 hours at 37°. The diametral tensile strength (DTS) was measured with the use of a Universal Testing Machine (United Calibration Corp., Garden Grove, Calif.) at a cross-head speed of 1 mm/min.
As a practical matter, the Ca/P ratio must remain above 1.67, or stoichiometry dictates the preparation of hydroxyapatite rather than tetracalcium phosphate. Therefore, in this context, "less than 2" should be interpreted herein to mean less than 2 but greater than 1.67.
Quenching of fired mixture in an anhydrous atmosphere:
After heating the mixture for a sufficient length of time, the mixture must be cooled down rapidly to prevent reversion of the tetracalcium phosphate to the phases that are more stable than tetracalcium phosphate at temperatures lower than 1400° C. If the tetracalcium phosphate were cooled down slowly, for example, by letting it cool down spontaneously in a furnace that has been turned off, the product obtained would contain little tetracalcium phosphate. Instead, it would be a mixture that would additionally contain hydroxyapatite, calcium oxide, α-tricalcium phosphate, β-tricalcium phosphate, or calcium pyrophosphate, depending on the Ca/P ratio and the rate of cooling. Such a sample, if used for preparing the cement, would yield a product with poor setting and strength properties. Therefore, quenching is necessary, and it must be done under a substantially anhydrous environment. One example of a suitable anhydrous quench technique would be to place the mixture, as soon as it is no longer red hot, in a vacuum desiccator to isolate the tetracalcium phosphate from moisture. Other techniques of anhydrous quenching available to those of skill in the art may be used.
If the tetracalcium phosphate is quenched in an atmosphere that contains moisture, a reaction illustrated by equation (9) or (10) will occur and the tetracalcium phosphate crystals will become coated with the reaction products, hydroxyapatite and Ca(OH)2 or CaO. Such a tetracalcium phosphate sample will have poor reactivity when used in the cement formulation.
Ca4 (PO4)2 O+H2 O→0.667 Ca5 (PO4)3 OH+0.667 Ca(OH)2 (9)
Ca4 (PO4)2 O+0.33 H2 O→0.667 Ca5 (PO4)3 OH+0.667 CaO (10)
Exposure to moisture at this stage will cause damage to the tetracalcium phosphate's reactivity to a significant extent, although not as critical as in the later stages of the preparation. This is because at this point, the tetracalcium phosphate is the form of chunks or lumps, with relatively small surface areas amenable to contamination, as compared with the tetracalcium phosphate that has been processed to a fine-particle state. However, moisture absorbed in the uncomminuted tetracalcium phosphate may produce an adverse effect in the comminution process as described below.
Particle size reduction.
To produce calcium phosphate cement with the desirable properties, sparingly soluble calcium phosphates of a variety and/or mixture of particle sizes may be used. For many applications, it is preferred that the tetracalcium phosphate have at least a substantial percentage of particles, e.g., at least about 10%, of median particle size of 15 μm or below. In some applications, such as formulating an injectable root canal filler, tetracalcium phosphate with a median particle size of 1 μm or below would be preferred. Therefore, the particle size of the tetracalcium phosphate prepared in Example 5 above needs to be reduced by mechanical means. A substantially anhydrous environment during the particle size reduction process is critical. Small samples of the tetracalcium phosphate may, for example, be comminuted by hand grinding in room air for a brief period, e.g., 5 min., but long exposure to room air would be unacceptable. If the tetracalcium phosphate is ground in a ball mill, it must be done in a closed container to isolate the tetracalcium phosphate from the large volume of moist room air, or in a non-aqueous liquid that has been made anhydrous. Some of the liquids that can be advantageously employed are cyclohexane, dioxane, and absolute ethanol. Other non-aqueous liquids may also be used. Traces of water in these liquids should be removed by molecular sieve or other suitable desccicants. Liquids that should not be used include water, 95% ethanol, other alcohol solutions that contain water, acetone (which generally contains some water), etc. If one of the latter liquids is used, the ground tetracalcium phosphate will contain poorly crystallized hydroxyapatite and calcium hydroxide or calcium oxide. Such a sample will produce a poor quality cement or a cement mixture that will not harden. Once the ground tetracalcium phosphate is exposed to moisture and the reaction products coat the tetracalcium phosphate crystal surfaces, the reactivity of the tetracalcium phosphate sample cannot be rejuvenated at this point by heating and removing the adsorbed moisture.
As mentioned earlier, if the uncomminuted tetracalcium phosphate contains absorbed moisture, because of the limited surface area, the damage to the tetracalcium phosphate's reactivity as a result of hydroxyapatite coating formation would be significant but perhaps not critical. However, when such a tetracalcium phosphate sample is comminuted in an anhydrous liquid, the moisture released from the contaminated tetracalcium phosphate into the liquid will facilitate the undesirable reaction depicted by equation (9) or (10). This usually will render the tetracalcium phosphate unusable for cement formulation. If it is suspected that the uncomminuted tetracalcium phosphate has been exposed to moisture, and it is to be ground in an anhydrous liquid, it should be heated at 200° C. for 24 hours to remove absorbed moisture and cooled to room temperature in an anhydrous environment before grinding.
Storage of ground tetracalcium phosphate.
It is important that the ground tetracalcium phosphate be stored in an anhydrous environment. Because the ground tetracalcium phosphate would have relatively large surface area, surface contamination by the reaction products with moisture will substantially compromise the reactivity of the tetracalcium phosphate and the quality of the cement. Once the surface contamination products are formed in substantial quantities, the reactivity of the tetracalcium phosphate cannot be rejuvenated by heating.
The detrimental effects of moist TTCP on the diametral tensile strength of the set cement are illustrated by Table II.
TABLE II______________________________________Diametral Tensile Strength of Calcium Phosphate CementPrepared with Tetracalcium Phosphate that Had Been Exposedto 100% Humidity for Different Lengths of TimeLength of Exposure Diametral Tensile Strengthin Days mean ± s.d. (n = 3) in MPa______________________________________0 10.38 ± 0.440.2 8.71 ± 0.101 7.85 ± 0.132 6.66 ± 0.255 6.26 ± 0.0716 2.63 ± 0.24______________________________________
Calcium phosphate cement powders were prepared by thorough mixing of 3.66 grams of tetracalcium phosphate and 1.36 grams of dicalcium phosphate. The tetracalcium phosphate had a median particle size of 10.2 μm and had been exposed to humid air for various periods as indicated. The dicalcium phosphate had a median particle size of 0.8 μm. The diametral tensile strengths were measured following the same procedure as described earlier.
FIGS. 1-3 also illustrate the formation of hydroxyapatite in TTCP exposed to moist air and its effects. FIG. 1 depicts by bar graph the diametral tensile strength of samples prepared as described above with a TTCP Ca/P ratio of 1.90, but with the indicated periods of exposure of TTCP to 100% humidity air at 37° C.
FIG. 2 gives the x-ray diffraction spectra of TTCP prepared from a mixture with Ca/P=1.90, and then exposed to 37° C. 100% humidity air for the indicated lengths of time. For the x-ray diffraction studies depicted in the figures, cement samples were first made into a fine powder form by hand grinding with the use of a mortar and pestle. Approximately 0.25 grams of ample was placed on the sample holder. A computer-controlled powder x-ray diffractometer (Rigaku, Danvers, Mass.) with CuKα radiation generated under the conditions of 40 kv and 25 mA was used to obtain the XRD patterns. Data were collected in the 2× scanning mode using a step width of 0.01° and count time of 2 sec. Growth of the hydroxyapatite impurity shoulder with increasing moisture exposure of the TTCP is illustrated.
FIG. 3 illustrates by x-ray diffraction spectra the formation of hydroxyapatite impurity in TTCP ground in 95% ethanol for 20 hours. 20 g of TTCP was ground in 50 mL of 95% ethanol in a 250 mL-size agate jar that also contained 50 1-cm diameter agate balls. The grinding was done with the use of a planetary ball mill (Retsch model PM4, Brinkman Instruments, Westbury, N.Y.) for a total of 20 hours. The ground TTCP was dried in a 70° C. vacuum oven for 2 days.
Additional properties of improved calcium phosphate cement as compared with the original calcium phosphate cement of Brown and Chow are listed in Table III:
TABLE III1______________________________________ Improved CPC (TTCP Ca/P = 1.90; Original CPC anhydrous prep) (TTCP Ca/P = 2.0)______________________________________Compressive 64.8 ± .8 MPa 36.0 ± .7strength (n = 3) (n = 5) (Fukase, 1990)2Diametral 13.1 ± 1.3 MPa 6.9 ± .3strength (n = 8) (n = 5)Setting time: 14 min. 25Gilmore needle (Brown and Chow,method 1986)3______________________________________ 1 Moles TTCP: Moles DCPA = 1:1, powder/liquid (by wt.) = 4.0, liquid phase = 25 mmol/L H3 PO4, testing conditions as per Example 4. 2 Fukase et al., "Setting Reactions and Compressive Strengths of Calcium Phosphate Cements," J. Dent. Res. 69(12):1852-56 (1990). 3 Brown, W. E. and Chow, L. C. (1988): A New Calcium Phosphate, Wate Setting Cement, Cements Research Progress 1986, P. W. Brown, Ed., Westerville, Ohio: American Ceramic Society, pp. 352-379.
As will be recognized by those of skill in the art, other specific techniques for preparation of the tetracalcium phosphate component of the inventive cement may be employed so long as the calcium to phosphate ratio of the tetracalcium phosphate is less than two, and/or the preparation (particularly once the tetracalcium phosphate has been comminuted) is substantially anhydrous. While either the recommended reduction in calcium to phosphate ratio or anhydrous preparation will improve the setting time and quality of the hydroxyapatite cement, the best results are obtained when both methods are practiced together. The inventive methods can be safely practiced in a laboratory or manufacturing facility without imposing excessive additional expenses. The new methods of preparation of tetracalcium phosphate produce cements with shorter and more consistent setting times and substantially greater mechanical strengths.
The inventive calcium phosphate cement is preferably prepared from the tetracalcium phosphate described above and one or more additional sparingly soluble calcium phosphates, particularly dicalcium phosphate anhydrous, dicalcium phosphate dihydrate, α-tricalcium phosphate, β-tricalcium phosphate, amorphous calcium phosphate, and octacalcium phosphate. Most preferably, tetracalcium phosphate is employed with dicalcium phosphate anhydrous or dicalcium phosphate dihydrate. The invention is practiced when the tetracalcium phosphate employed with the second sparingly soluble calcium phosphate compound is prepared in accordance with these conditions whether or not it is generated in situ from other precursors or passes through chemical intermediates. These compounds are contemplated as part of the inventive composition regardless of the nomenclature used to identify them, e.g., "calcium deficient calcium phosphate compounds" instead of dicalcium phosphate.
The specially prepared tetracalcium phosphate and other sparingly soluble calcium phosphate compound(s) are combined with a liquid phase to form the useful cement, paste or slurry. The liquid phase is aqueous at least in part and may typically be water, saline, blood, dilute phosphoric acid, or one of the above with the addition of up to 10% of a calcium or phosphate source in the calcium phosphate cement powder or in the liquid phase itself. In situ liquid, e.g., at a wound site, can suffice.
Additional calcium phosphate cement compositions that consisted of TTCP prepared in accordance with the invention and one other calcium phosphate from the group consisting of α-tricalcium phosphate (α-TCP), β-tricalcium phosphate (β-TCP), amorphous calcium phosphate (ACP), and octacalcium phosphate (OCP) were prepared with a liquid phase of 1.5 mol/L Na2 HPO4. This phosphate level in the liquid phase can be attained by adding up to 10% of a phosphate salt in the calcium phosphate cement powder as described in U.S. Pat. Nos. Re. 33,161 and 33,221. Properties of calcium phosphate cements that consisted of TTCP and a calcium phosphate other than DCPA or DCPD are given in Table IV below.
TABLE IV______________________________________ DTS2, MPa setting timeSolid component P/L1 (mean ± s.d.; n = 3) (min)______________________________________TTCP3 + 2 α-TCP 3 1.29 ± .26 25TTCP3 + 2 β-TCP 3 0.22 ± .17 90TTCP3 + 2 ACP 2.5 0.98 ± .11 153 TTCP3 + 2 OCP 3 0.48 ± .06 90______________________________________ 1 Powder to liquid ratio (by weight) 2 Diametral tensile strength 3 Ca/P = 1.90
The above calcium phosphate cement formulations, while not preferred because of their relatively low strengths, did harden. Some improvements in strengths are likely with adjustment of particle size, powder to liquid ratio and other parameters. These formulations did not set quickly, e.g., 2 hours, when water, saline, or a dilute phosphoric acid was used as the liquid phase in place of the 1.5 mol/L Na2 HPO4.
Generally, the preferred cement will be comprised of an equimolar mixture of tetracalcium phosphate and dicalcium phosphate, although TTCP/dicalcium phosphate ratios may range from 1:1 to about 1:4. Calcium phosphate cement that has a TTCP/DCPA ratio of 1.0 will have the stoichiometry of hydroxyapatite. Experimental data now show that cement setting can occur when the ratio is as low as 0.33 or lower. Furthermore, the presence of excess DCPA does not lead to residual DCPA in the end product; the product is apatitic, probably a calcium deficient apatite that has poor crystallinity and greater solubility. Such material may have different in vivo characteristics from that of stoichiometric hydroxyapatite produced by calcium phosphate cement with a TTCP/DCPA ratio of 1.0, perhaps resorbing more rapidly in bone.
The inventive cement may be supplied to the user in a variety of forms, including as powders or as a powder mixture which is later mixed with a diluent such as water or blood to make putty; or as a pre-mixed putty which may contain a nonaqueous extender, e.g., glycerin and/or propylene glycol. It may be supplied with or in the instrumentation which is used to introduce the cement into the body, for example, a syringe, percutaneous device, "gun", cannula, biocompatible packet, dentula, reamer, file, or other forms which will be apparent to those of ordinary skill in the art. It is contemplated that the cement, in any of these forms, may be made available to the surgeon, veterinarian or dentist via a kit containing one or more of its key components. The cement is generally provided or employed in a sterilized condition. Sterilization may be accomplished, e.g., by gamma-ray radiation, typically at a dose of 2.5 Mrad.
The inventive cement may be employed in a variety of medical, dental and veterinarian procedures to substitute for missing or defective bone or tooth tissue. For example, the cements of the present invention may be used in place of any of the cements known in the prior art as: (1) cavity bases and liners to protect the pulp, (ii) materials for capping exposed pulps, (iii) materials to replace or promote regeneration of bone mineral lost due to periodontal disease, (iv) direct filling materials (may be temporary) that have physical properties similar to enamel and are adhesive to enamel and dentin, (v) a cement to build up alveolar ridges in edentulous patients, (vi) an endodontic filling material for root canals, (vii) a material to cement retention pins, (viii) a material for filling sockets after a tooth extraction, (ix) a replacement of bone that has been removed surgically or lost due to trauma, (x) a cement for implanting or replanting teeth, (xi) a luring cement in dentistry and orthopedic surgery, (xii) an investment mold material, (xiii) a material which will promote bone mineral in its vicinity, (xiv) a remineralizing polish for use in place of pumice, and (xv) a root cement for remineralizing and desensitizing of exposed root surfaces, (xvi) a cement for orthopedic prostheses, (xvii) a tooth implant, (xviii) a device for percutaneous passage of tubes, wires and other medical instruments through the skin, and (xxix) a replacement material for bone loss due to abscess. Slurries of calcium phosphate cement may be used to repair bone damage caused by osteoporosis. Reconstruction of cleft palate and other congenital skeletal defects is contemplated with use of the inventive cement, as are other forms of reconstructive and cosmetic surgery.
Various additives may be included in the inventive cements, slurries and pastes to adjust their properties and the properties of the hydroxyapatite products made from them. For example, in addition to the calcium and phosphate containing compounds and dilute acids and bases which may be added to adjust the Ca/P ratio and pH; proteins, medicaments, supporting or strengthening filler materials, crystal growth adjusters, viscosity modifiers, pore forming agents and other additives may be incorporated without departing from the scope of this invention.
The novel implants thus prepared are also contemplated as part of the present invention. Where such implants contact living bone tissue, it is believed that the lack of fusion of the hydroxyapatite crystallites resulting from the setting reaction of the inventive cement allows osteoclasts to slowly resorb the implants over time. The implants are sufficiently resistant to resorption, however, so that the osteoclasts appear to regard the implants as disorganized bone rather than a synthetic material. Because of this, the implant is slowly resorbed as compared with other calcium-based cements, thus leaving woven bone deposits in its stead.
Since the inventive cements are fully compatible with living tissue, they are especially advantageous where contact with living tissue is necessary. Clinical use of the inventive cement is illustrated in the following example:
A seventy-year-old female patient suffered from chronic sinus disease so advanced it had dissolved a quarter-sized portion of the bone of her forehead. The inventive calcium phosphate cement was prepared from an equimolar mixture of tetracalcium phosphate and dicalcium phosphate powders mixed with water. The tetracalcium phosphate employed had a Ca/P ratio of 1.90 and was prepared and maintained under substantially anhydrous conditions. The weight ratio of powder to water in the cement was between 3.5 and 4.0, with a small amount of additional liquid being supplied by bodily fluids at the wound site. The resulting cement paste was molded intraoperatively to fit the sinus defect, resulting in a successful skull repair. The patient was discharged from the hospital within three days, and on follow-up retained the sinus patch, with evidence of steadily regenerating bone replacing the implant. Other similar results were obtained in repairing bony defects of additional patients.
As the inventive materials possess remineralization capabilities, the discussion above with respect to the use of the inventive compositions as cements is fully applicable to their use as remineralizers. The two main differences between the inventive remineralizers and the inventive cements are particle size and solid-to-liquid ratio. For use as a cement, the calcium phosphates are ground to specific particle sizes (e.g., relatively large TTCP and small DCPA) to achieve rapid setting and high strength, whereas for a remineralizer, the particles are ground to sizes to produce optimum release of calcium and phosphate ions into saliva and plaque to affect remineralization. Additionally, for preparation of the cements, the calcium phosphate particles are combined with much less liquid so that a paste is formed, rather than a slurry. An example of a chewing gum which utilizes the inventive composition to provide an oral slurry with remineralization potential follows.
A chewing gum with remineralization potential is prepared by blending the calcium phosphate cement powder (Ca/P of TTCP=1.90; moles TTCP/moles DCPA=1.0) into a commercially available gum base at a 5% by weight level by hand mixing. Test subjects who chewed the calcium phosphate cement gum were sampled every two minutes up to a total of 16 minutes for the pH and calcium and phosphate levels in their saliva. The calcium and phosphate levels and the degree of supersaturation with respect to tooth mineral were found to be elevated to significantly higher extent and for a longer period than those produced by a prior art chewing gum that contained 7.5 wt % dicalcium phosphate dihydrate. Pickel et al., "The Effects of a Chewing Gum Containing Dicalcium Phosphate on Salivary Calcium and Phosphate." Alabama Med. Soc. 2:286-287 (1965). Similarly, the inventive compositions may be delivered e.g., via a dentifrice, rather than a chewing gum.
While the primary benefits of the present invention are believed to relate to dental, medical and veterinary applications, it is also contemplated that the techniques may be employed in conjunction with an industrial hydroxyapatite cement, for example, to repair damage, e.g., from corrosion, to marble and other stone articles.
It should be understood that the foregoing disclosure emphasizes certain specific embodiments of the invention and that all modifications or alternatives equivalent thereto are within the spirit or scope of the invention as set forth in the appended claims.
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Snowfall In Kashmir Prompt Authorities To Issue Avalanche Warning
Boats are moored to the bank of Dal lake after a snowfall on February... News PhotoHorizontal,Human Interest,India,Jammu and Kashmir,Lake,Nautical Vessel,Snowing,SrinagarPhotographer Yawar NazirCollection: Getty Images News 2013 Yawar NazirSRINAGAR, KASHMIR, INDIA - FEBRUARY 23: Boats are moored to the bank of Dal lake after a snowfall on February 23, 2013 in Srinagar, Indian Administered Kashmir, India. Several parts of the Kashmir Valley, including the summer capital Srinagar, experienced fresh snowfall today, prompting the authorities to issue an avalanche warning and leading to closure of the Jammu-Srinagar Highway, the only road link between Kashmir and rest of India. (Photo by Yawar Nazir/Getty Images)

subset: commoncrawl


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If the game freezes, just click inside it (games can get unresponsive if you click elsewhere on the page).
Your task in this colorful and fast paced game is to fly through the space matching your color with the background and staying alive for as long as you can. A series of colors will approach you from the right. When you hit the color hold down corresponding ARROW KEY to rack up points. If you aren't holding the right key your health is decreasing as you go and once it reaches zero, it is game over. The fields move faster as time progresses. Good luck!
Use arrow keys to play the game.


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MMA News
TUF Live Ratings | Episode 9 Marks Slight Improvement Following Lowest Rated Episode In History
By Jamie McAllister
TUF rebounds with a slight increase in viewers following the lowest rated episode in the shows history the previous week.
Episode 8 received just 929,000 viewers & episode 9 last week received 954,000 viewers. Marking a slight increase in interest following the decline.
The episode featured the final opening round match-up featuring Mike Rio vs. Andy Ogle. Ogle secured the second round submission over Rio and claimed the final spot and moving Team Faber into a lead of (5-3).
Dana & UFC executives are said to be satisfied with the ratings however changes will be made before "TUF: Live 2″ later in the year.
While on Spike TV "TUF" averaged 1.7 million viewers before it was moved to FX due to the deal with FOX & this seasons premier only received 1.3 million viewers.
8 Responses to "TUF Live Ratings | Episode 9 Marks Slight Improvement Following Lowest Rated Episode In History"
Cuz it's getting old. Less gayness more fighting. What is this like the 15th season now. Plus I stopped watching after fabers team got punked. And the lack of talent makes it hard to watch
After looking at ratings history, at least for the last few recent seasons, I don't see an average of 1.7 viewers throughout the entire season like what indicated in the article. Episodes peaked that high, but 1.3-1.5 was pretty normal the last few seasons.
I think I speak for a lot of people in the reason im not watching it is usually because its on a friday night and i'm usually out. If they changed the day its on to like monday or something, then it would be watched more often.
Very true.
Yeah for sure. agree with ZACK…after faber thought it was a good idea to be gay and punk the other team…no pun intended, i realized i could get better UFC coverage on FUEL…..Dont we have enough small guys already…The UFC should do more heavyweight and LHW…..Contact ever college football drop out and of course mma outlets, boxing, wrestling, etc and pursuade them with the chance of contract…It seems easy give us more talented big guys..Hell pay me and ill be there fighting prolly getting knocked out but
Why would a drop out football player be good in Mma? And there are plenty of LHW and HW do you watch UFC?
Do you watch TUF at all? the last season that LHW were in was season 8 and the last season HW were featured was season 10… its now season 15. Since then there has been one middleweight season and that was season 11, meaning the last four seasons have been 170 or lower, meaning more litte guys. Next two seasons should be L and HW imo
*LHW and HW not L and HW
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Tags hard rock, rock, alternative rock, punk rock
Artists Ra, Dommin, Anberlin
August 16, 2011
For the cold fusion spats of hate, ratcheting you apart like a body on the rack. Emotional lactic acid boils in the corners of your eyes, angry red crescents forming on your palms as your fists curl tighter and tighter, looking for the release only fists on flesh can provide.
Fax by NocensLupus
At midnight, a heartbroken man walks into a basement lounge.
jazz, vocal jazz, torch songs, blues
Adamo by NocensLupus
Doctor's orders: Draw a warm bath, pour a glass of wine, and spend the evening dreaming of the man who makes your heart stutter.
jazz, vocal jazz, big band
Tempestas by NocensLupus
When the clouds roll in across the prairie, slow and dark.
blues, rock, blues rock
Pulvis by NocensLupus
A hot wind blowing through yellowed grass, the smell of wildflowers and manure filling the summer air.
alternative country, country, folk, bluegrass


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Continuing Education . Classes
Portfolio Preparation
Course No. YADR 700
Cost $375 Register Now
Sessions 10
Grades 10-12
Room 200
Instructor Eddie Mitchell
Dates Session 1: June 15-June 26, Session 2: July 27-August 7 (M-F) – 9:30am12:30pm
This course will help you to put together a stronger portfolio needed in applying to art colleges, as well as the fabulous benefits of improving your drawing skills, the joys of trying different drawing materials, along with showing you what an art college is actually looking for in your portfolio. Besides enjoying the classroom explorations and drawings assigned outside the classroom, you will get to engage in the occasional critique in a fun and informative way. The goal of this course is to help you reach a higher level of skill in the creation of your own artwork. Parent permission is required for life drawing because of nude models.
Still Life Painting
Course No. CEPT 140 00
Cost $325 Register Now
Sessions 8
Room 302
Dates June 13 - August 8, no class July 4 (Saturdays) – 2 - 5pm
Using oil paints and traditional methods, students will develop 2 different paintings on canvas of various still life arrangements. This class is beneficial for any level of artist. The beginner will learn basic drawing, composition, color theory, and paint handling. The intermediate to advanced will greatly benefit from a refresher course in fundamentals. The style and techniques taught and demonstrated will be grounded in realism, however expressive brush strokes and Impressionist styles are encouraged.
Stop Motion Animation/Claymation
Course No. YAAN 300
Cost $325 Register Now
Sessions 10
Grades 7-12
Room 317
Instructor Adrijana Wichert Nerone
Dates Session 2: July 27-August 7 (M-F) – 12:304pm
Learn how to bring your creative storytelling to life visually, through stop-motion animation! You will write, draw, sculpt, paint, take photos, and edit! If you like to make up stories, take pictures, and make artwork using mixed media, this class is for you! We will begin our class by watching many funny, serious, and amazing stop-motion animations by a variety of artists and learn to recognize and put into effect the principles of animation. Working with a partner or individually, you will make up a short story and write it down. You will learn how to draw an effective storyboard to help tell your story visually. Then you will create your sets and characters using a combination of paper, clay, objects, toys, paint, etc. You will follow your storyboard to shoot your animation using your digital camera and tripod. We will edit and create sound for our animations using Final Cut. We will experiment with pixilation, claymation, paper animation, and object animation. Armatures and tie downs will be utilized to make your character magically walk or dance. You will create 1-3 animations each depending on your ideas. Get ready to have some fun! You will take home your animation(s) on a disc. Please bring your own digital camera and tripod.
Studio Foundations
Course No. YAFD 135
Cost $325 Register Now
Sessions 10
Grades 9-12
Room 201
Instructor Terry Clark
Dates Session 1: June 15-June 26, Session 2: July 27-August 7 (M-F) – 14pm
In this introduction to drawing and painting in the studio environment, exposure to basic concepts and materials will offer you a strong foundation on which to build. The essential tools of an artist are the pencil and brush. You'll use both, separately and combined, to generate multiple exercises and images. The elements and principles of color, perspective, shape, shading, and pattern are explored through projects. All of the projects will be guided by individual and written instructions. Every new challenge and concept will promote both your artistic confidence and vocabulary.
Studio Painting in Acrylic
Course No. CEPT 425 00
Cost $325 Register Now
Sessions 8
Room 306
Dates June 9 - July 28 (Tuesday) – 6:30 - 9:30pm
This studio painting course will help guide you toward developing individual ideas within your work while broadening your painting vocabulary and skills. Through discussion and demonstration you'll learn concepts and techniques to use as you create your work. We'll focus on developing the ability to work at an independent advanced level. Open to intermediate to advanced students.
The Spinning Wheel
Course No. CEFM 200 00
Cost $375 Register Now
Sessions 8
Room Praxis Fiber Workshop
Dates June 11 - July 30 (Thursday) – 6 - 9pm
The practice of spinning fibers to form thread and yarns has been in existence for over 10,000 years. The spinning wheel itself is believed to have evolved in India 1,000 years ago. During this course, you can master this timeless craft through developing a working knowledge of hand spinning on a spinning wheel. In handspinning, you can design the exact kind of yarn you desire with any variations in texture, color, or thickness that you wish that can be used towards weaving, knitting, crocheting, and embroidery. You will first work with wool and cotton then move to your material of choice-it can be ribbon, patterned cloth, or yarn from your discarded sweaters. We will also work in the dye lab to customize your material. This is a project driven, hands on course-great for the material minded who might also have an interest in color and pattern. Experimentation is encouraged! No previous spinning experience is necessary
Upcycled Hand + Rod Puppets
Course No. CEFD 130 00
Cost $250 Register Now
Sessions 6
Room 301
Dates June 10 - July 15 (Wednesday) – 6 - 8:30pm
Who hasn't been touched by Jim Henson's Muppets? Use upcycled and found materials to create characters to play with and talk through. Once your new characters are finished we will team up with classmates to formulate a performance for the last session. Props and a visible setting will be available for rehearsal and performance. Be prepared for a light potluck reception for the final evening-performance.
View Camera: Black & White Large Format Photography
Course No. CEPH 250 00
Cost $300 Register Now
Sessions 6
Room 315
Dates June 15 - July 20 (Monday) – 6:30 - 9:30pm
This is an introductory class for photographers with a desire to use the view camera and large format photography in their work. The coursework covers 4×5 and 8×10 camera operation, large format sheet film, the zone system, darkroom printing skills, related equipment, and individual projects using the large format image. In addition to technical work specific to the view camera, this class focuses on traditional darkroom printing methods. Students learn to choose and handle appropriate equipment and materials, develop large format sheet film, and make fine prints on gelatin-silver papers. Each student will develop and produce a final portfolio of archival gelatinsilver prints. Available for use are 4×5 and 8×10 view cameras, light meters, darkroom equipment and chemistry. Students will need to supply their own 4×5 and 8×10 black & white sheet film and gelatin-silver papers (20×24 maximum paper size). Basic understanding of 35mm camera operation and exposure principles recommended.
Take a look at our current course catalog!
Learn about NEXT, CIA's day-long event designed to help students learn more about pursuing a career in art or design.
Experience the life of an art student at CIA through this 2-week residential program.


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You know you've become your mother... or older sisters... when...
You talk about your "Programs" on tv! So, here I go... I just LOVE the new show Emily Owens, M.D.! Have you seen it yet? Tuesday nights on the CW... just two episodes have aired and I'm already hooked! I find the star, Mamie Gummer (daughter of Meryl Streep... and she looks just like her) absolutely wonderful! She's both funny and smart... and her acting is so good! You can seriously tell that she not only got her looks, but her talent from her mother.
I originally just tuned in to see if Mamie was any good... curious to see if she came close to her mom. Well, she has blown me away and the whole story line is pretty good, too. If you've ever been the geek in high school, you can truly relate to the character! And if you're a Meryl Streep fan, you will find yourself just mesmerized by how much Mamie looks like her! I swear, it's Kramer vs. Kramer de ja vu!
So... I reccommend that you check out Emily Owens, MD, next Tuesday night... it's been Curly approved! (I really should drop Meryl a note...)
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"I so love this place."
"She can turn a code red to a totally fab fresh new look."
"Patti is one of the greatest hair stylists in the Dallas/Ft. Worth area."
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Be Fabulous Blog
Time For The Next Level
Model Tiara Rogers stops by Duke's Hair Studio to take this latest photoshoot to the next level. The team spent all morning prepping Rogers for the shoot but the end result was a tons of great looks for the camera. Patti Duke, once again flexed her styling muscles with 4 fresh new looks. Wardrobe was [...]
5 Tips to Stay Fabulous
5. Leave all chemical service to the trained professionals. Your hair will thank you. 4. If you must use a flat iron, manage temperature gage accordingly. Low heat is a must. NO EXCEPTIONS. 3. Have a light moccran oil to maintain your tresses. Depend on your style artist for instruction only. 2.Keep a hydrating shampoo [...]
Beauty All-Access: Top Eye Shadows
ESSENCE's glam squad test drives the fiercest eye shadows in this week's round table. Read more: http://www.essence.com/2012/04/27/beauty-all-access-top-eye-shadows/#ixzz1vwVgGKZF
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Invigorating shampoo/ hydrating conditioner to suit your tresses need, design style of your choice
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Tuesday, September 20, 2011
Can Someone Wake up Mike Whan?
As you probably heard, a 16-year-old named Lexi Thompson won her first LPGA event over the weekend, becoming the youngest player by two years to win on the LPGA Tour.
And this is great news to just about everyone it seems, except the suits with the LPGA. Why? Because they still haven't granted Thompson full status on the LPGA Tour. Yep. A current winner in 2011 isn't a full-time member, and won't be, because she's too young and has to go through Q-School.
Again, let me repeat that - a winner on the LPGA Tour that is 16 is being asked to go through Q-School after beating all the big names in a competitive tournament last weekend.
Now, I've met Mike Whan, and I really enjoy him. He's a super nice guy that has done some great things for the LPGA and continues to move the tour forward in the right direction, but even Albert Pujos strikes out, and it seems Whan is with this decision.
I understand the age requirements (well, not really ... the LPGA can use any boost they can get, so why wouldn't they just let anyone try to be a full-time member no matter their age? Isn't any coverage good coverage?), but Lexi won. She won! And she's really, really talented! And despite the numerous examples of young people flaming out, it seems Lexi is the real deal, as real a talent as we've seen at a young age since Michelle Wie (who took much longer to win her first event).
Whan needs to change this. Golf has always been performance based. If you win, you're in, no matter what. Look at Jason Gore. Look at "Tin Cup." Look at just about anyone that has played themselves into a competitive position and succeeded. Lexi might have to go to Q-School after proving herself at the most elite level in women's golf. What more do you want, Mike? For her to make a cut with the boys? I'm pretty sure if you keep shunning her away, that'll be the next place you see her, and all that does is help the image of Lexi Thompson and hurt the image of the LPGA.
Change this, please. I have enough stuff giving me headaches these days.
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1 comment:
- Will said...
I agree. This is stupid, but if the glass is half full --- she will breeze through Q-School and, for the first time ever, LPGA Q-School might actually get some viewers! Which, is LPGA QSchool even on tv!? This question coming from a pretty big golf fan!
- September 20, 2011 at 12:46 PM
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text: This book didn't make it under many Christmas Trees, surely for it's price alone but this over 30 pound, 336 page book would make any Star Wars geek squeal in delight. It's a book of blueprints and production drawings from all of the Star Wars movies. It looks absolutely gorgeous as shown in the website for the book here. At $1,000 for a hand numbered version or $500 (Amazon.com has it for $450) for the limited edition, it's a budget blaster for most who can only dream geek dreams about this beautiful book.


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Page Eye Center has a full service optical service center which offers the latest styles of frames. Brands sold but not limited to are, Oakley, Harlesy Davidson, Bebe, Sketchers and many others.
Contact Lenses are also prescribed and sold at Page Eye Center. Contact Lens brands sold include and not limited to, Air Optix, Acuvue, Biofinity, Purevision and Proclear. Toric lenses, Quarteryly and Yearly Replacements contacts can also be purchased.
Comprehensive eye exams for all ages are offered. Medical and Emergency eye exams and foreign body removal are also offered. The latest equipment such as a fundus camera and Cirrus OCT whichare used to diagnose and assess the overall health of the eye.
Page Eye Center
124 6th Ave
Page, AZ 86040
Office Hours:
Monday - Friday
Call and Make Your
Appointment Today
Dr David Mallavia is a graduate of Idaho State University and received his doctorate degree at the Southern California College of Optometry in Fullerton , CA .
Dr Mallavia has been practicing at the Page Eye Center since the summer of 2004. He is a member of the American Optometric Association and the Arizona Optometric Association. The Page Eye Center is affiliated with Banner Hospital in Page, AZ


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Bath & Body Works Semi-Annual Sale
Bath & Body Works' Semi-Annual Sale just started this morning! Happy shopping!
Discussion and debate are highly encouraged, and we expect community members to participate respectfully. When asking a question, please check the FAQ section (above) for information about purchasing, price, dupes, and the like. If you have general feedback or need technical support, please contact us.
Comments that include advertisements, self-promotion, insults, etc. may be in violation of our comment policy and subject to deletion. Please see our comment policy for more information.


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A Striped Armchair
Babbling About Books (Katiebabs)
Beth Fish Reads
Beyond Books (Cat)
Boob Tube
Bookalicio.us (Pam)
Book Binge
Book Bound
Books, Books and More Books (Nath)
Book Faery (Tori)
Book Labryinth
Book Lovers Inc.
Book Lurve
Book Secrets (Diana)
Book Smugglers
Breezing Through
Capricious Reader (Heather)
Coffeehouse Banter (Rowena)
Damn Heart... (Sayuri)
Dear Author
Devourer of Books
Dreaming in Books (John)
Emily's Reading Room
Estella's Revenge (Andi)
Everyday Reader (Sarah)
Fantastic Book Review
Fiction Vixen
Flight into Fantasy (Shannon)
Galley Smith (Michelle)
Gemini's Gems (Linda)
Glossamer Obsessions (AnimeJune)
Hanging With Bells
Heidenkind's Hideaway
Hooked on YA Books
Hope's Bookshelf
I Just Finished Reading (Lori)
Ink and Paper (Jo)
Janicu's Book Blog
JoJo's Book Corner
Kelley's Korner
La Femme Readers
Larissa's Bookish Life
Laurie's Laudanum
Leontine's Book Realm
Love to Read For Fun
Lurv a la Mode (Kmont)
Lusty Reader
Mama Kitty Reveiws
Me and My Books (Li)
Monroe With a Twist
Musings of a Bibliophile
Nobody Asked Me (Rosie)
Nocturnal Wonderings (CindyS)
Nose in a Book (Lisabea)
Opinionated Me?
Pearl's World of Romance
Peace Love & Pat - Book Review
Ramblings of a Book Bitch
Ramblings on Romance, etc. (KristieJ)
Read this Book! (Kate)
Reading in Color (Ari)
Renee's Book Addiction
Romance Rookie (Jill)
Smach Attack Reads
Smexy Books (Mandi)
Smitten With Books
Smokin' Hot Books
Snark & Bark
Sophistikatied Rewviews (Katie)
Sparrow Review
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Supernatrual Snark (Jenny)
That's Queen Bitch to You
The Adventures of an Intrepid Reader (Marg)
The Book Lush
The Book Muncher
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The Bookish Type
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The Last Blog in the Universe
The Lit Connection
The Misadventures of Super Librarian (Wendy)
The Naughty Book Kitties (Brent)
The Page Flipper (Chelsea)
The Story Siren
The Sweet Bookshelf
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The Way I See It (Zeek)
Thrifty Reader (Ames)
Tynga's Reviews
We Love YA
What Were You Expecting (Holly)


text: To my fellow CIO's the real question here is the question behind the question. The Old school CIO's, and I know a number of them, are Analytical and Reserved, but this does not answer the real question here. The Business and IT environments today are far from this black and white. The CIO in today's market needs to answer the question behind the question this way. Yes the CIO need's to be Analytical and some what Reserved, but in today's fast moving environments the CIO need to bring to the table and out going attitude and personality and be able to engage Executives from other areas of the business, and not only to engage but bring viable solution to the Business. So today's CIO needs a lot of the Out Going and Engaging personality but also have the ability to maintain that Analytical and Reserved composure when need be. Well that's my take on the question and I could be wrong but I don't think so with nearly 30 years experience in Business and IT.


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With football season yet to officially launch, LeBron's Instagram is more entertaining than an average Marlins game featuring Billy the "I fell off the wagon" Marlin. Red means click.
After LeBron got his police escort in trouble by posting a video on Instagram a week ago, the King continues to entertain the digital world. The latest is a photo of James and Greg Oden working out in Heat gear…
Next we have LeBron running on an anti-gravity treadmill typically reserved for aging, rehabbing types like Kobe Bryant. It must be to make Oden feel more welcome.
Finally, here's LeBron acting silly outside of what looks to be American Airlines Arena.
One more week til' football.


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You are here
Smartphone Photography Apps
Smartphone Photography Apps
Event Date:
Tuesday, July 8, 2014 - 7:00pm to 8:45pm
Learn how to use the camera's settings and controls. You'll learn about apps for editing, stylizing, and posting your photos. Please bring your fully charged smartphone. George LeClaire, Daily Herald photographer, is the instructor.


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Going for the Gold: A Medal for Mom
Annemarie Blanco June 30, 2015
Adnan Gutic is working hard to take the top spot in judo to honor his late mother
U.S. Paralympic National Team Qualifies for Rio 2016
U.S. Soccer June 30, 2015
The men's 7-a-side soccer team wins over Argentina at the world championships
Norman and Pruitt break distance world records in Indianapolis
Brianna Tammaro June 28, 2015
Grace Norman sets two world marks at Indy International and Fast Cow Invitational
Going for the Gold: 10 Questions with table tennis Paralympic medalist Tahl Leibovitz
Annemarie Blanco June 25, 2015
Twenty-year table tennis veteran Tahl Leibovitz shares his secrets to success heading into Toronto
Ten Paralympians nominated for 2015 ESPY Awards
Katie Branham June 24, 2015
U.S. Paralympians nominated for Best Male and Female with a Disability ESPY awards
Going for the Gold: John Kusku chases goalball perfection
Annemarie Blanco June 23, 2015
Veteran men's goalball player John Kuzku is ready to take Team USA to the podium
Toast Of Champaign: U Of Illinois Wheelchair Athletes Shine At Nationals
Stuart Lieberman June 22, 2015
Twenty-two athletes with Illinois ties competed at the event this past weekend
A.J. Digby Races To The Forefront Of Next U.S. Paralympics Generation
Stuart Lieberman June 21, 2015
Just 17, Digby is a rising star in both track and sled hockey.
Records fall on final day of U.S. Paralympics Track and Field National Championships
Brianna Tammaro June 21, 2015
T20 distance runner Michael Brannigan breaks world and American record in men's 1500-meter at nationals
Athletes wish their dads a Happy Father's Day
Annemarie Blanco June 21, 2015
Athletes share some special moments with their dads in celebration of Father's Day


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Grades have no direct impact on the overall score.
Free Form Studios is a photographer's archive of photos that celebrate the natural beauty of nude women. The softcore site explores the erotic sensuality of these beautiful amateur models, for just $15 for the first month and $10 each additional month.
Exclusive softcore collection.
These are all exclusive scenes featuring sexy young amateurs looking awesome while au naturale. They get fully nude in hot tubs, on beds, and outdoors, smiling at the camera while sharing it all with the camera. You will see spread shots but that's about as far as they go. The main draw is simply enjoying the beautiful amateurs in their natural state.
Good number of galleries.
Free Form has been updating regularly for nearly eight years now and they've built a nice collection of photos in that time. There are currently 505 galleries online, for a total of around 25,000 images. Not bad for exclusive niche material like this.
High quality photos.
The photos here are great-sized, at over 3400 x 2300. They're generally sharp and nicely done, while still maintaining somewhat of an amateur feel to them. It's really an interesting combination of high quality artistic and amateur niches and it works well for them.
Other Good Stuff:
Very basic design and navigation.
The set-up here is extremely simple. They list the scenes in the order they were added, around 8 to a page and there's a model index, but that's it. The model index is awkwardly displayed in a table that doesn't really fit. In fact, the whole site is text and tables and that's about it. The design and navigation would both benefit from an upgrade.
Minor Negatives:
The pictures are sexy and good-sized but the site is awfully basic.
Free Form Studios fills a unique niche by offering high quality artistic amateur material. The pictures look very good and they do an excellent job at staying true to the niche. The site, on the other hand, takes the whole "amateur" thing a bit too far. It's badly in need of a redesign and restructuring. Still, at this price for this much exclusive content, I won't be too hard on them! Fans of amateur erotic will want to check out this quality and affordable site.
About the Content:
Downloadable exclusive photos and videos of sexy amateur models in solo softcore scenes.
Download Managers:
Yes, should work.
Channel Max: 8
Able to pause/resume.
Test Software: Speed Download
Download Speed:
Download Mgr: 3.7MB/sec.
Browser: 900KB/sec.
(30MB video, 20Mbps cable internet)
Exclusive Info:
Advertised: 100% exclusive.
My Opinion: Yes, these are original scenes you won't find anywhere else.
File Sizes (HQ):
(average size, HQ)
HD Video:
No HD quality videos.
Live Cams:
No free live cam shows.
Logging In:
Only user/pw required.
Videos don't require pw.
Model Appearance:
Mix of white and ethnic models.
Mostly amateur-looking.
Body types from thin to average.
Model Info:
110 models total.
Ages 18-30.
Mostly U.S. based.
Other Content:
No notable extras.
Pic Details:
Professional level photography.
Little to no airbrushing.
Good lighting, bright colors.
Pic Dimensions (HQ):
Large: 3400 x 2300
Medium: 1000 x 667
Sizes vary a little.
Streaming Player:
No in-browser playback available.
Updates in Last 7 Days:
1 image gallery.
(on par with previous updates)


text: Teaching the technique Jan. 30, 2013 @ 05:50 PM Will Doran Login Subscribe or link to print subscription Wesley Beeson | The Sanford Herald Wesley Beeson | The Sanford Herald Local artist Lisa Mathis, center, teaches students Jake Brower, right, Carolyn Chipman, left, and Nancy Findley, second from left, watercolor techniques as artist Beverly Brookshire, third from left, looks on Wednesday during an Adult Watercolor Class Workshop at the ArtStudio on Steele Street. Wesley Beeson | The Sanford Herald Lisa Mathis applies a watercolor underpainting during the workshop. More Fewer photos SANFORD —


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Takes you through the process of making a Drupal website that automatically tailors and sizes content for a wide range of displays, from desktops to mobile devices.
Create and edit custom themes in Drupal 7 and migrate existing themes built in Drupal 6.
"The quality of the videos and teaching is excellent and rarely a week goes by when I do not sign in and learn something new." —Brian L.
more from our members »


text:
Health care is a world that's constantly changing. Medical research and technological discoveries combine to form a steady stream of new diagnostic tools, new techniques, new drugs, new procedures—even unmanned robotic surgery.
When Nelson Ebo '12 performed his first solo opera recital in New Hampshire this past March,
you would never know from listening to his
powerful tenor voice and seemingly effortless
delivery how difficult his journey was to that stage.
Maybe you recall Jim Ford '04 from basketball games in the early 2000s. He was the especially audacious Howie the Hawk who leaped off the bleachers to stir up fans.
South African sprinter Oscar Pistorius, a double amputee who wears custom-made running "blades" when racing, captured the world's attention when he challenged officials for his right to compete in the 2008 Beijing Olympics. Read more


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This Moodhouse Podcast makes me wanna rub vegetable oil all over my body and deep fry myself!
%s1 / %s2
Wednesday night while the rest of Hollywood was over checking out The Flaming Lips second night at Hollywood Forever Cemetery show, I was at the El Rey watching James Vincent McMorrow open up for the Civil Wars. There's something special when an artist steps on a stage with just their guitar these days. So many artists, and not that I am against it, step on stage with all their electronic equipment to add in extra background effects with their guitar. James stepped out into a softly lit stage at the El Rey and took the crowd into a trance from the first echo of his voice. The El Rey has always been a favorite venue of mine from the minute I moved into my first apartment down the street over 5 years ago. My favorite shows were the super intimate, dimly lit shows, and this one was no different. James' voice which I originally compared to the likes of Bon Iver, which still holds true, shed light on another musical comparison at certain notes, Jeff Buckley. I know this is no easy comparison, as Buckley's voice was one of a kind, but McMorrow's voice draws the crowd silent and captivated everyone in the El Rey without a doubt. My favorite part of the show was when JVM unplugged his guitar, stepped away from the mic, and sang what is my favorite song off his album, If I Had a Boat. I can't remember the last time that I saw an artist do that, abandoning all the electronic sound carrying devices, and just singing unplugged. It was so quiet you could hear a pin drop, as he closed the night out before the Civil Wars would come on. I didn't stick around for that part, how could I, nothing was going to be like what James Vincent McMorrow just dropped on the packed El Rey. Plus, I was there to see him anyways, not the opener. It's not everyday that happens. Check out his tour, if he hasn't already come through your city, make sure you get your tickets now. Special thanks to Jamie from Vagrant Records for helping make all of this happen.


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Finding great insurance at an excellent price just got easier. With more than 65 years of experience, and a highly trained, service-focused staff, Bruen Deldin DiDio Associates Inc. is one of the region's leaders in insurance services.
As an independent insurance and bonding services agency our sole obligation is to our customers. Rather than represent one provider, we work with many of the country's top-rated insurance companies, so we can give you the options you need and secure great rates for you.
Whether you require commercial insurance for your business, bonding services for a construction project, personal insurance for your home or car, health and life insurance for your employees, or something else, we'll find you the best policy or service for the best price.
Access to top-notch insurance companies for home, car, and personal property protection. Click here to learn more.
Find innovative insurance solutions tailored to the unique way your business works. Click here to learn more.
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Did you know…that BDD'S Health Insurance and Employee Benefits Department is licensed and certified in Health Care Reform Exchange plan coverages, by the Department of Insurance in CT and NY. Contact us today to have one of our knowledgeable agents review all of your Individual /Family or Group Health Plan Exchange options.
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Did you know that April is National Distracted Driving Awareness Month.
Check out our insitiful artilces below.
Did You Know that April is Distracted Driving Awareness Month?
Distracted Driving…Why Risk It?


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Winter Indoor Activities Stay Busy Regardless Of Freezing Temperatures
Presque Isle offers many indoor activities, which are especially great during the winter months. Despite the freezing cold weather we have been experiencing, businesses say they have been busy. Kids running all over at The Maine Jump in Presque Isle is not uncommon this time of the year.
"We typically see in the colder temperatures people bringing their kids in after a storm, because everybody for safety reasons, have been cooped up inside so they want their kids to be able to exert some energy and get some of those wiggles out." Jenna Spoto, co-owner of Maine Jump Presque Isle.
Another great activity is ice skating at the Forum. It's not only a great workout but it's a lot of fun as well. Even when there are subzero temperatures outside, Skate Guard Morgan Wilcox says business is not effected.
"It's not quite as cold in here, but it's still a winter activity so lots of people are coming," said Wilcox.
A business that is definitely not striking out on cold days is Northern Lanes Bowling Alley.
"Increase in business with cold weather, they like to come in, get inside and do something where it's warm,"said Richard Fletcher, a mechanic at Northern Lanes Bowling Alley in Presque Isle.
Regardless of temperatures dropping, these businesses have kept busy and continue to do so all winter long.
Category: News


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Death Cannon
this wiki
Death Cannon (デス・キャノン, Desu Kyanon) is a Soul Resonance move used by Death the Kid and his twin guns Patty and Liz in Kid's Execution Mode. The move charges Kid's wavelength and after a countdown fires a huge ball of energy at his opponent from his twin cannons which explodes when it reaches the target and leaves nothing but a plume of skull shaped smoke. The extent of the blast is so powerful that the resulting recoil, is enough to blow Kid several inches back.
In the anime, in episode 6 Kid's Death Cannon wasn't fatal to Soul and Black Star, since he didn't use Death Cannon like in a real battle.
Once again in the anime, during the final fight against the Kishin, Asura, Kid uses a variant of this technique after the all three of The Lines of Sanzu connect. Instead of the usual two cannons that form on his arms, two large barrels appear. They are much larger in size, gold and stand on the end tips of the skulls (that looks similar to Shinigami's mask) that are located on the outer side of each. Due to it's size and the fact that it requires these 'feet' to stand, this is a one-hit attack. The attack itself involves firing two powerful beams at the target, one red and the other green. However, even with all three Sanzu Lines connected and the immense energy this technique fires, it was still unsuccessful in destroying the Kishin, but manged to force him to revert to his true form rather than the large form he had assumed previously.


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- Attorney General Brad D. Schimel
- Fighting Crime
- Victim Assistance
- Consumer Protection
- Media Center
- About Department of Justice
- Topical Index
This Google™ translation feature is provided for informational purposes only.
The Office of the Attorney General is unable to guarantee the accuracy of this translation and is therefore not liable for any inaccurate information resulting from the translation application tool.
Please consult with a translator for accuracy if you are relying on the translation or are using this site for official business.Contact the Department of Justice
MADISON - Attorney General Van Hollen issued the following statement regarding Governor Doyle signing the Wisconsin Crime Alert Network into law:
I applaud Governor Doyle for signing Senate Bill 533, public safety legislation authorizing the creation of the Wisconsin Crime Alert Network at the Department of Justice, into law. I would also especially like to thank Senator Jeff Plale and Representatives Ann Hraychuck and Garey Bies for authoring the legislation.
This bill authorizes the Department of Justice to implement and operate the Wisconsin Crime Alert Network. The fax and email network system would enable local law enforcement to alert participating businesses of criminal activity or notify them of a missing person. The alert can be tailored to specific types of businesses and geographic regions in order to provide the most useful information to those who are voluntary members of the network.
Public safety should be the number one priority for state and local governments. The Wisconsin Crime Alert Network is an example of creative thinking that allows us to achieve public safety goals efficiently and effectively without creating new tax burdens, especially while state and local governments face budget shortfalls. We can solve more crimes, prevent more criminal activity and safely recover more endangered missing children and adults - all without raising taxes or imposing involuntary fees.


text: If you play soccer, you know people are constantly juggling on sidelines, at practice, etc. Even though juggling is a simple task, not a lot of people can consistently do it for a long period of time without messing up. Like anything in sports, if you want to be great, you need to have rock-solid fundamentals. Check out this video ...Continue Reading →


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Operating Guidelines
Announcements of openings for new Steering Committee members will be circulated via SETAC email notifications, with nominations sent to the Steering Committee for review and confirmation of willingness to serve. Balance of sectors (government, industry, and academia) and geographic location (Canada, United States, and Mexico) will be maintained.
Steering Committee
Alan Jones, 2015 CSC Chair, Oregon State University
Katie Albanese, Student Representative, The Ohio State University
Craig Butt, Duke University
Wendy Hillwalker, SC Johnson
John Kucklick, National Institute of Standards and Technology
Robert Letcher, Environment Canada
Jonathan Martin, University of Alberta
Angela Perez, ChemRisk, LLC
Pamela Rice, U.S. Department of Agriculture
Amina Salamova, Indiana University
Daniel Snow, 2015 Past Chair, University of Nebraska
Ping Sun, 2015 Chair-Elect, Proctor and Gamble
Elin Ulrich, U.S. Environmental Protection Agency
Sascha Usenko, Baylor University
Charles Wong, University of Winnipeg
How To Become a Member of the AG
Previous winners:
2014- Jonathan Challis
2013- Rachel Marek
2012 - Eleanor Robinson
2011 – Chelsae Rochman
2010 – Dianna Delach
2009 – Jiafan Wang and Zhe Lu
2013- Rachel Marek
2012 - Eleanor Robinson
2011 – Chelsae Rochman
2010 – Dianna Delach
Previous Winners:
2014- Ching- Hua Huang
2014- Ching- Hua Huang
2013 - Rockie Yarwood
2012 - Cora Young
2011 – Yo Chin
2010 – David Atwood
2009 – Jon Chorover and John Rimoldi
2013 - Rockie Yarwood
2012 - Cora Young
2011 – Yo Chin
2010 – David Atwood
Chemistry Advisory Group File Archives
Steering Committee Minutes
Register Early for SETAC Salt Lake City and SavePosted in Annual Meetings, Monday, June 29, 2015The early bird catches the worm – and a 20% discount! Plan ahead and register today for five days of cutting-edge science in environmental toxicology ... more »
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The Nothing That Is: A Natural History of Zero, by Robert Kaplan.2000, Oxford University Press, 198 Madison Avenue, New York, New York 10016, paperback, 225pp, $9.95. ISBN 0-19-514237-3. (800)-445-9714 or http://www.oup.com/
Just when it might seem that nothing new could be written about zero, and that all puns on it were exhausted, along comes a book that happily does a lot of the former and, mercifully, little of the latter. Robert Kaplan's book, The Nothing That Is: A Natural History of Zero, is a fascinating view of the concept and numeral from many angles.
We learn that the Sumerians, who partially used positional notation based on 1, 10, and 60, employed something like zero at the center of their numbers. Next we see that the Greeks never used the zero in the way we do but that they still constructed large numbers and built beautiful buildings geometrically. When the author introduces the Greeks, he begins his discussion on the origin of the shape of the modern numeral and establishes why it is a hollow oval. Later, about halfway through the book, he tells us that the Arabs supplied its name sifr, a translation of the Hindu word for nothing. The Hindus are given credit for incorporating the concept into arithmetic within the decimal system; the Chinese do not get it and the author takes pains to explain why. On the way there are excursions into the life of the Maya – they too used zero – and we get a clear description of their astronomic calculations and calendar that alone is worth buying this book for.
The author traverses ground well known to math historians, with a richness of language and expression that can be illuminating, irksome, novel, and massively entertaining. The reader might occasionally groan under the semantic weight of phrases like "philology captured ontogeny in taking its time to recognize negatives" or "the gallimaufry of numbers", but will also be rewarded by the vast range of ideas and people that are presented. We learn about the links to Mayan gods and their human sacrifices, the contribution of Fibonacci, fractional exponents, sections of Florentine contract law, Pierre de Fermat, Leibniz and Newton, the Bernoullis, theology, astronomy, logic, and the hypothesis of Gödel. There is an elegant exposition on graphs and the limit-based definition of the derivative. The final chapters are philosophic essays centering on such concepts as: the vacuum in nature, eugenics and non-existence, all are delivered with rich expression and imagery. Ultimately we become aware that "…each of us singly and together has entertained an angel unawares."
The author writes for a general audience but one with plenty of time to sit, read, and absorb the material. If in retirement, put down that copy of War and Peace for something truly amusing and educative. This is a history for people with brains.
Austin Lobo, Professor, Washington College, Chestertown, MD