A deodorizing composition formed by an aqueous solution of divalent metal ions, preferably zinc ions, and i) an anionic alkylaryl alkoxy carboxylate/carboxylic acid surfactant and/or ii) an anionic alcohol alkoxy carboxylate/carboxylic acid surfactant.

1. Field of the Invention
The present invention relates to as aqueous formulation that substantially reduces odors. In particular, the invention relates to an aqueous solution of divalent metal ions, most preferably zinc ions, and an anionic alkoxy carboxylate/carboxylic acid surfactant.
2. Related Background
Offensive odors are a common problem. For example, offensive odors can emanate from contaminant materials, decaying materials, or incompatible materials. Even when such materials have been substantially removed, offensive odors can continue to be noticeable because of the high olfactory sensitivity of people. Further, offensive odors are caused by a variety of materials in a variety of environments. Thus, different deodorizing applications have varying requirements. Accordingly, there is a continuing need for deodorizing compositions to substantially eliminate offensive odors.
Attempts to ameliorate offensive odors include the use of perfumes to mask such malodors. U.S. Pat. No. 5,490,982 describes a cosmetic microemulsion compositions that is formed by two immiscible liquid phases containing isoeicosane, water, a fragrance, and a fatty glyceride ester alkoxylated with alkylene oxide such as alkylene oxide alkoxylated caprylic/capric fatty glyceride ester. U.S. Pat. No. 4,938,416 describes a water based fragrance dispersion that includes a fragrance oil and a fragrance enhancer such as an alcohol, ester, ketone, aldehyde, acid, terpene, ether, or other complex materials. A preferable nonionic surfactant such as nonylphenol polyoxyethylene or polyoxyethylene sorbitan monooleate can be included.
Other attempts to form a composition that deodorizes include U.S. Pat. No. 5,076,960 which describes an aqueous composition containing alkali metal halogenites such as sodium chlorite, a salt of a transition or post transition metal such as zinc chloride, and an alcohol to assist in stabilizing the sodium chlorite. The composition can include a perfume, in which case the perfume can be stabilized against the alkali metal halogenite by the use of an anionic surfactant. U.S. Pat. No. 4,963,287 also describes a cleaner composition which includes an alkali metal halogenite, a perfume, and an anionic surfactant to stabilize the perfume. International Patent Publication WO 95/15186 and European Patent Publication EP 0 401 140 B1 describe deodorizing compositions containing aldehydes.
U.S. Pat. No. 4,840,792 describes a composition for neutralizing bad smells utilizing a compound that is an aliphatic alcohol, aldehyde, aliphatic ketone, aliphatic ester, aromatic lactone, phenol, aromatic ether, amine, or an aromatic amine. U.S. Pat. Nos. 4,946,672 and 4,818,524 describe deodorizing compositions containing imino (HNxe2x95x90) moieties such a polymeric biguanide. U.S. Pat. No. 3,172,817 describes deodorizing compositions containing a beta-diketone.
British Patent No. 941,105, and U.S. Pat. Nos. 2,544,093, and 3,074,891 describe deodorizing compositions containing esters of alpha,beta-unsaturated monocarboxylic acids. U.S. Pat. No. 5,089,258 describes deodorizing compositions containing citric acid and a monovalent salt of citric acid. U.S. Pat. No. 5,211,870 describes deodorizing compositions containing a zeolite. International Patent Publication No. WO 91/12029 describes deodorizing compositions containing zeolite and an absorbent gelling material.
U.S. Pat. No. 4,983,578 describes deodorizing compositions containing hydroxyphosphoric acid, polyalkylene glycol alkyl ether, alcohol,and perfume. U.S. Pat. No. 4,909,986 describes aqueous deodorizing compositions containing a water-soluble organic polymer having a carboxyl group and its ammonium salt. Organic monobasic acids and their salts may be included. The salts may include alkali metal salts, calcium salts, iron salts, ammonium salts and alkanol/alkanol-amine salts.
Insect repellents can present unpleasant odors. Further, repellents can be more effective if the applied surface is better coated. Accordingly, repellant compositions can contain perfumes and surfactants. U.S. Pat. Nos. 4,696,676, 4,933,371, and 5,196,200 describe repellents formed from alcohols such as 1-nonen-3-ol and linalool, while U.S. Pat. No. 4,449,987 describes a fragrant insect repellent composition that includes methyl heptenone, coumarin, and an indole. Perfumes and surfactants may be included in these insect repellant compositions.
European Patent Publication 0 386 714 describes the use of monoterpenes such as borneol, isoborneol, camphor, and isobornyl acetate as a deodorizer and insect repellant.
Deodorants can be in the form of an aerosol composition. U.S. Pat. No. 3,159,535 describes an aerosol composition that is a liquid/liquid/gas three phase composition which includes an emulsifier which can be anionic, cationic or nonionic. Particularly suitable emulsifiers include long chain fatty acid esters of polyhydrocylic compounds such as the glycol, glycerol and sorbitol esters of oleic, stearic, palmitic and lauric acids; and ethoxylated fatty acids and amides. U.S. Pat. No. 3,974,270 describes an aerosol composition using a water soluble poly-lower alkoxylated cetyl alcohol such as cetyl propoxylate as a vehicle for aluminum chlorhydrate. European Patent Publication No. 0 032 779 describes water-based aerosol compositions containing dimethylether, perfume, and an ethylene oxide/propylene oxide block copolymer surfactant.
Zinc compounds have been used in oral and dental compositions to reduce calculus formation and to inhibit offensive mouth odors. U.S. Pat. No. 4,469,674 describes a composition containing zinc salt and a soluble ionic fluoride salt. U.S. Pat. No. 4,325,939 describes a composition containing an alkali metal zinc citrate or ammonium zinc citrate.
U.S. Pat. No. 4,138,477 describes a composition, to control mouth odors, containing a combination formed from a zinc salt and an anionic polymer. The anionic polymer includes carboxyl, sulfonic or phosphonic acid groups with which the zinc ion reacts.
Many attempts to control odor utilize cyclodextrin or derivatives of cyclodextrin. U.S. Pat. Nos. 3,426,011, 3,453,257, 3,453,258, 3,553,191, 3,565,887, 4,535,152, 4,638,058, 4,616,008, 4,678,598, 4,727,824, 4,746,734, 5,102,564, 5,234,610, 5,234,611, 5,578,563, 5,593,670, 5,663,134, 5,668,097, 5,714,137, 5,783,544, Japanese Patent Nos. JP 58-124452, JP 61-128973, JP 63-164953, JP 3-170415, JP 2-251681, JP 1-256597, JP 1-256596, and JP 3-284616, and International Patent Publications WO 89/02698 and WO 96/04940 describe particular perfumes, cyclodextrins, derivatives of cyclodextrin, and various compositions containing cyclodextrins, and/or its derivatives. Additional ingredients such as metallic salts such as zinc salts, anionic polymeric soil release agents, alkali carbonates and bicarbonates, clays, and surfactants are also described. U.S. Pat. No. 5,663,134 states, however, that when metallic salts such as zinc salts are utilized, anionic surfactants are not preferred because water-insoluble salts can form.
As described above, surfactants are desirably included in deodorizing compositions used for many applications to assist in forming a complete, uniform coverage of the malodorous substrate by the applied composition. Surfactants can be described as cationic, nonionic, or anionic in accordance with their ionic properties, well known to one in the art. Anionic surfactants have a negative valence charge and are generally provided in association with a cation. When divalent cationic zinc is used in deodorizing compositions, nonionic or cationic surfactants are conventionally used in order to assure that the zinc ions remain in solution.
U.S. Pat. No. 4,902,434 describes a dry granular composition, for the neutralization of odors and the removal of soil, formed from a divalent transition metal salt coated onto a solid inorganic granular carrier effective to bound malodorous materials to the surface of the carrier which then can be removed along with the dry granular carrier. Anionic surfactants such as sodium lauryl sulfate and magnesium lauryl sulfate can be used.
Without being bound to theory, it is believed that zinc ions in solution are more readily available to react with malodorous odor molecules than are zinc ions in a solid form (as a salt). Accordingly, it would be desirable to form a deodorizing composition that contains zinc ions in aqueous solution, together with an anionic surfactant that imparts improved flow and coating properties to the solution while maintaining the zinc ions in solution, to facilitate reactions of the zinc with malodorous molecules.
The present invention is directed to a deodorizing composition comprising an aqueous solution of divalent metal ions, preferably zinc ions, and an anionic surfactant. The anionic surfactant is described by the formula Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)Xxe2x80x94Oxe2x80x94CH2COOxe2x88x92, wherein R is a fatty alcohol substituent or an alkylaryl substituent. The fatty alcohol substituent is a residue of a C6-C20 fatty alcohol, the alkylaryl substituent is a residue of a C10-C20 alkylaryl compound, and X is at least 2. The metal divalent metal ions are present in a concentration that is effective to deodorize a substrate to which the solution is applied. The anionic surfactant is present in a concentration effective to maintain the metal ions in solution.
The aqueous solution of this invention advantageously may be a clear solution that can be formulated so that its application to a substrate in a deodorizing effective amount does not leave a visible residue on the substrate.
The invention is also directed to a method to deodorize a substrate, comprising the step of applying the above-described deodorizing composition.
The present invention is directed to a deodorizing composition that is an aqueous solution containing divalent metal ions and an anionic surfactant. The divalent metal ions are preferably copper or zinc, and most preferably zinc ions. The anionic surfactant is described by the formula Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)Xxe2x80x94Oxe2x80x94CH2COOxe2x88x92, wherein R is a fatty alcohol substituent or an alkylaryl substituent.
There should be at least two moles of the ethoxylate for each mole of surfactant moleculexe2x80x94that is, X should be at least 2. Preferably, X is from 2 to 20, most preferably, X is from 5 to 15.
When R is a fatty acid substituent, R should contain from 6 to 20 carbon atomsxe2x80x94that is, R should be formed from a C6-C20 fatty alcohol. The fatty alcohol substituent provides hydrophobic functionality to the surfactant, balancing the hydrophilic functionality of the poly(ethylene oxide) carboxylate. Surfactants containing fatty alcohol substituents having carbon numbers below 6 disadvantageously are unlikely to provide adequate film forming and surface wetting properties.
When R is an alkylaryl substituent, the alkyl portion(s) should contain from 4 to 14 carbon atomsxe2x80x94that is, the overall alkylaryl substituent should be a C10-C20 substituent.
The anionic surfactant described by the formula Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)xxe2x80x94Oxe2x80x94CH2COOxe2x88x92, wherein R is a fatty alcohol substituent, can be called an alcohol ethoxycarboxylate. The alcohol ethoxycarboxylate can be supplied associated with any convenient cation such as for example, H+, Na+, K+, or NH4+. Any suitable convenient alcohol ethoxycarboxylic acid or alcohol ethoxycarboxylate can be used such as, for example, NEODOX(trademark) alcohol ethoxycarboxylic acids from Shell Chemicals, Houston, Tex., and SANDOPAN(copyright) carboxylated surfactants from Clariant Corporation, Charlotte, N.C.
The anionic surfactant described by the formula Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)xxe2x80x94Oxe2x80x94CH2COOxe2x88x92, wherein R is an alkylaryl substituent can be called an alkylaryl ethoxycarboxylate. The alkylaryl ethoxycarboxylate can be supplied associated with any convenient cation such as for example, H+, Na+, K+, or NH4+. Any suitable convenient alkylaryl ethoxycarboxylic acid or alkylaryl ethoxycarboxylate can be used such as, for example, SANDOPAN(copyright) MA-18 carboxylated surfactants from Clariant Corporation, Charlotte, N.C.
The preferred divalent zinc ions can be supplied by any convenient source such as, for example, zinc chloride, zinc acetate, zinc bromide, zinc acetate, zinc salicylate, zinc propionate, zinc gluconate, zinc lactate, zinc maleate, zinc sulfate or zinc nitrate.
The zinc ions should be in the amount of from about 0.01 wt % to about 5 wt % of the total aqueous deodorizing composition. Preferably, the zinc ions should be in the amount of from about 0.02 wt % to about 2 wt %, more preferably from about 0.03 wt % to about 0.3 wt %. All percentages recited herein are weight percentages unless specifically stated otherwise.
The required anionic surfactant(s) used in the inventive composition advantageously provides multiple functions: i) as an emulsifier for added fragrance ingredients, ii) as a wetting agent, iii) as a control release agent for the zinc, and iv) as a deodorizer itself. The first two properties are apparent. In regard to the third property, without being held to theory, it is believed that the control release agent properties of the surfactants of the present invention derive from the interaction of the anionic surfactant with the zinc +2 cation. It is believed that the zinc is lightly bound (weakly chelated) to the anionic surfactant. Thus, the zinc is sufficiently bound to maintain its solubility, yet sufficiently weakly bound so as to be available for reaction with malodorous molecules. It is believed that zinc reacts with the reduced sulfur compounds, such as thiols and disulfides, and amines that are often present as malodorous molecules. The zinc binds with the malodorous molecules to lower the volatility of the malodorous molecules, thus reducing and eliminating odor. Further, the anionic surfactant itself can react with malodorous molecules such as amines to reduce odor.
The pH of the aqueous composition of this invention should be acidic to about very slightly basic. Preferably, the pH should be from about 3 to about 8. More preferably, the pH should be from about 4 to about 7. Most preferably, the pH should be from about 4 to about 6. In general, a lower pH helps maintain solubilization and availability of the zinc cation.
Accordingly, another important function of the acid form of the anionic surfactants of the invention is to adjust the pH of the aqueous solution. The anionic surfactants of the invention can be used as a mixture of suitable anionic surfactants. Thus, a mixture of ethoxylated carboxylic acids and ethoxylated carboxylates can be used to conveniently adjust and control the solution pH. For example, a 1:1 mixture of SANDOPAN(copyright) DTC acid and SANDOPAN(copyright) LS-24-N have been conveniently used to control pH at about 5 or below.
The weight ratio of zinc to surfactant should be from about 1:2 to about 1:40. The anionic surfactant of the present invention should be from about 0.005 wt % to about 10 wt % of the total aqueous solution. Preferably, the anionic surfactant should be from about 0.2 wt % to about 1.0 wt %, and more preferably from about 0.50 wt % to about 0.75 wt %.
Other compatible constituents can be included in the aqueous formulations of this invention. Perfumes can be included to mask odors and to impart a pleasant fragrance to the solution. Miscible cosolvents such as, for example, isopropyl alcohol (isopropanol), ethanol, propylene glycol, or mixtures thereof can be included. Such cosolvents conveniently include, for example, glycol ethers such as Rxe2x80x94(OCH2CH2)xOH, wherein R is a methyl, ethyl, propyl, butyl or hexyl substituent, and x is 1 or 2, and the corresponding propylene oxide based glycol ethers represented by the formula Rxe2x80x94(OCH(CH3)CH2)xOH, wherein R is a methyl, ethyl, propyl, butyl or hexyl substituent, and x is 1 or 2. Such cosolvents can be included, for example, to assist in drying of the applied solution. Compatible colorants can be included to impart a pleasing color or to identify areas that have been treated with the aqueous solution. Various organic and inorganic acids may be included for pH control. Any other suitable compatible additive can be conveniently included such as, for example, preservatives, antifungal agents, and bacterial control agents.
The aqueous solution of the invention can be applied by any convenient method such as, for example, by spraying, wiping, pouring, or dipping. The application can be from any convenient applicator such as, for example, a pump spray container, an aerosol spray container, a sponge, a cloth, a synthetic composite applicator, a bottle, or a tray.


A power plant using sea waves comprising a float, a horizontal shaft. The float (1/1) of a spherical or cylindrical shape made with plastic or metal material, empty filled with ballast, floats half emerged and transfers the wave vertical motions to a vertical metal beam (1/2) which can be increased or decreased in order to deal with the tidal changes of the sea level. The vertical beam is attached with knuckle joins, at one end with the float and at the other with horizontal beam of rectangular metal triangle which transfers the vertical motions at the horizontally moving forwards and backwards saw (1/5) with the two chains (1/6) and (3/20) which rotate two pairs of gears each gear of a pair to the diametrically opposite side, so that with every movement one gear produces action while the other gear of the pair moves freely. The gears rotate the horizontal shaft which is fitted on them (3/8) and the shaft gives motion to the generator.

The new method, which is invented, is based on previous invention Nos. WO 99/014489-(HATZILAKOS) and U.S. Pat. No. 6,269,636 (HATZILAKOS).
The new converter has completely new technical characteristics, different functions and new innovations. Here are some basic differences from the previous invention:
The float instead of firm connection with the vertical metal beam is connected with knuckle joint. Another knuckle joint connects the upper end of the vertical metal beam with the horizontal beam.
The two knuckle joints of the vertical metal beam, give the required flexibility to the float so that during its up-down motions it is not following a curved track but follows vertical straight line.
This is a significant advantage because the cages are not in an elliptic but in a circular form and the cage is not a very complex construction but it is formed by only four vertical rails like these used for the railways. This secures the float and gives necessary stability.
Another important innovation is that the transfers of the vertical motions of the float are made directly rotational via the use of the invented metal rectangular triangle instead of the use of the biparallel level. With this innovation, the saw is not moving vertically but is moving horizontally on the ground forwards and backwards on rails without burdening the unit with its weight.
Instead of the shields placed on the gears, a second pair of gears is added in order to assist the chains to embrace much better the first pair and to avoid the disengagement. Between this mechanism and the generator, there are devices for the amplification and stabilization of the revolutions at the desired level.
The advantages of the new converter can be summarized as follows:
A. Reduction of the Cost:
1. The number of the metal parts are reduced from 5 to 4
2. The length of the vertical metal beam from 3.9 m is reduced to 2.5 m
3. The height of the unit is reduced from 3 m to 1.5 m
4. The height of the building for the roofing is reduced from 3.40 m to 1.7 m
5. The total length of the metal beams is reduced from 12.85 m to 9.15 m
6. The well for the saw is not needed
7. The base of the biparallel is not needed
B. Increase of the Productivity:
1. The maximum movement of the float is increased from 2.50 m to 3 m
2. The angular movement of the horizontal level is increased from 60° to 105°
3. The weight of all moving parts of the units is significantly reduced
This new invention is simple in its construction. It does not require any configuration of the seabed. It is simple and inexpensive in its operation. It does not require big waves in order to function. The application is feasible along coastlines or even in the ocean. The electric current output is direct, without any need for intermediate energy storage of any form. The transfer and conversion of the vertical motion of the sea surface, upwards-downwards is converted into a rotational motion directly to the electrical generator. Finally it is possible and easy to place a number of energy units in a series in order to form group of identical units and groups of units, which permit the standardization and mass production.
The waves of the sea move a float vertically up and down. Thus, the float rises to the crest and descends to the hollow of the wave, in a vertical upwards—downwards recalling motion. When the wave crashes against a pier, jetty or breakwater, then the reflection proportionally increases the potentiality of the wave. The entire unit has mechanisms which convert the vertical motions of the float, to horizontal and immediately to rotational directly to the electrical generator.
This sea wave energy converter, from the float to the electrical generator, forms one unit with the following main components:
1. The float (FIG. 1/No 1).
2. The vertical metal beam (2) attached to the float with knuckle joints (19).
3. The metal rectangular triangle which transfers the up-down vertical motions of the float into horizontal movements. The two perpendicular metal beams of the triangle at both ends are connected with the beam which is parallel or coincide to the hypotenuse for greater resistance to the forces exercised by the float,
4. The triangle's support mounting acting as a fulcrum (4).
5. The saw, a metal beam turned in its two ends (5) moving retrogressively in the horizontal level on rails, which keep firmly the horizontal motions.
6. Two gear chains similar to those used in a bicycle, attached to each end of the above mentioned beam, which we have named "saw". Stretched with the assistance of special stretchers (FIG. 3/16) they give the impression of a horizontally moving saw with the two chains in the place of the metal dented blade (FIG. 1/6).
7. Two pairs of gears on which the chains act, converting the horizontal movements of the saw to rotational (7). The gears, like the gears used in a bicycle, can move producing action towards one direction and freely towards the other (7).
8. The two shafts (FIG. 3/7 and 8) on which the above mentioned pairs of gears are fitted, two per each shaft. Special bases (bearings) support the shafts (FIG. 4/9).
All these components form one unit. Many units placed in parallel and side by side, form a group of units (FIG. 4). In these groups, each unit can operate independently on its own generator or operate together with another unit, in a common shaft and common generator. In this case the movements of the floats of a group can be liken to the operation of a multi-cylinder automobile engine, with many advantages from which the most important is that they use sea water instead of the polluting, inflammable, explosive and very expensive fossil fuels.
Construction and Function of Each Main Component of the Unit
The float is a plastic or metal pot, bulk or material. The diameter or the size of the float depends on the unit's desirable output. The floats have an opening in the top (10) which is used for the injection of a quantity of ballast, concrete or other heavy material (FIG. 2/11) such as to allow the float with all components of the unit to stay afloat, half-immersed in the water. In the upper part of the float there is a knuckle joint (1/19). In plastic floats, a metal beam is fitted inside the lowest part and connects the base with the knuckle joint at the top in order for all the parts, (the metal beam, the ballast, and the float) to become one body. The rest of the gap in the interior of the float is filled with light waterproof material in grains as felisol (2/14). This material, soaked in a special adhesive fluid, is compressed in order to become a compact body. This way, there is no room left for water to enter, which could otherwise possibly get into the float should it crack. The opening is sealed to become entirely watertight. The knuckle joint of the upper part of the float, connects the float with the one end of the vertical metal beam, while the other end is connected with the end (towards the sea) of the metal beam of the triangle, so that the float, the vertical metal beam and the metal triangle are moving as one part at the same time. The length of the vertical beam is convertible, so it can be modified to conform to the tidal changes of the sea surface level. The two knuckle joints of the vertical metal beam, give the required flexibility to the float so that during its up-down motions it is not following a curved track which necessarily follows the horizontal beam of the metal triangle (1/3). This metal triangle transfers the vertical up-down motions of the float, converting them to horizontal motions. The other end of the triangle, which also follows curved track (1/26), is attached to a metal arm (1/15) in order to align the motions at the end of the horizontal saw. These motions are converted to rotational movements by another mechanism.
The saw is moving forwards and backwards on rails without burdening the mechanism with its weight. At the two ends of the saw, two chains are fitted and with the use of stretchers (3/16) or with any other kind of similar mechanism, the pressure exercised on the gears is regulated so that the chains will neither become loose and get out of position, nor be in danger of breaking. The springs absorb all vibrations from the sudden changes of direction of the float, particularly in cases of rough sea conditions. When the springs are half way compressed, this is an indication that the chains are adequately taut.
The horizontal movements of the saw with the chains are converted to rotational by another mechanism (1/7) and (3/7). The chains engage the gears A and B (3/6) of the mechanism each one on the diametrically opposite side in order to avoid disengagement. In every motion of the float, one gear rotates with dynamic energy, while the other gear rotates moving freely. Thus, when the float is going up, the saw with the chains is moving horizontally towards the land (3/20). In this case, one chain rotates the gear A towards the direction (a) with dynamic energy, while the other chain rotates gear B to the opposite direction (b) freely. When the float is going down, the saw with the chains is moving towards the sea and one chain rotates gear B to the direction (c) with dynamic energy, while the other rotates the gear (A) to the opposite direction (d) freely. Thus, with every movement of the float, whether big or small upwards or downwards, the shaft rotates and activates the generator. The same applies with the second pair of gears, with the difference that the chains here engage the gears on the diametrically opposite sides in relation to the first pair (3/6). The only purpose of the second pair is to assist the chains to embrace much better the first pair and to avoid the disengagement. Between this mechanism and the generator, there are devices for the amplification and stabilization of the revolutions at the desired level.
If a problem arises in any chain and the whole unit must be immobilized, then a mechanism is activated and automatically leads the float on the upper end position where it remains locked. This mechanism is also used to immobilize a unit during scheduled maintenance works, without interrupting the operation of the other units of the group. In a case of an expected sea storm with strong wave conditions, all units of the group can be locked and secured. For such cases, the mechanism is activated automatically by sensors when the height of the waves exceeds the predetermined limits. The same mechanism returns the unit to normal operation when wave conditions return to normal.
Because extreme wave conditions appear in a limited period of time, in relation to the annual productive period, the design of such units should be based on normal wave situations, provided that in extreme conditions the operation of the units can stop. Avoiding heavy construction, the cost can be reduced.
The length of the two perpendicular beams of the metal triangle, are determined on the basis of the desired productivity of a unit but it should be taken under consideration that, as much as the length of the beam is increased towards the sea, and it decreases the vertical beam, then for bigger motions of the float, we have smaller motions of the saw, with bigger pushing force. On the opposite, as much the length of the vertical beam towards the land increases and the beam towards the sea decreases, for smaller motions of the float, we have bigger motions of the saw, but with smaller pushing force. However it is essential, that the entire mechanical system of the unit be balanced when the float is half immerged in the water. For small variations of this rule, the adjustment can be done with a counter weight (1/28) or with springs (1/18) which are stretched when the metal triangle is moving towards the sea. Such balance problems are reduced to the minimum when all components are made with light but equally durable materials, plastic (fiberglass) or duralumin. By using such material we have an additional advantage of protection from corrosion.
For improved system performance, the floats are restricted inside metal cages (4/21). These cages keep the floats in a restricted space, so that they will not be carried away by the waves. The cages do not impede either the vertical motion of the floats or the free passage of the seawater. These cages are made by metal tubes or rails according to the size of the float and the expected wave conditions in the area. Four rails like those used on railways, are placed vertically and crossed around the float, on the inner walls of the recess of the pier or breakwater or any coastal construction we may use for the converter (FIG. 4). The concrete piers are preferable because, as it is clearly proven, the effect of the piers double the energy of the incident wave and they offer a steady support for positioning all components of the unit.
The float is surrounded on its top and bottom sections with additional horizontal rubber or metal belts (1/29) for the protection from damages occurring from the attrition as sliding on the four vertical rails of the cage. These protective belts are removable by revolving them on the horizontal level periodically, whenever damages are noticed. Belts are replaced when they are totally ruined. The vertical metal beam (1/2), with the two knuckle joints (1/19) gives the float the flexibility to slide up-down inside the cage like a piston inside its cylinder.
The cage is the most important component of this sea wave technology, and is the main element of durability of the converter. The cage protects the float from the horizontal movements due to pressures of the waves. When the float is firmly protected inside the cage and the cage inside the recess of the pier, then all the forces are transferred smoothly and the converter is functioning secured even in extreme wave conditions. Without cages, floats are carried away and destroyed even with moderate winds of 2-4 Beaufort.
For a better productive function of the unit, the converter should be placed from 1.5 to 2.0 meters above the average sea surface on the pier and about 3.0 to 4.0 meters above the seabed. These limits depend on the prevailing wave condition in the area. Each unit, normally functions independently from other units; however its function can also be combined with the adjacent unit so that one or more units can act on a common shaft (4/8). Thus, the added energy does not increase the speed of the rotation but the power which can easily be converted to the required speed. When more than one unit acts on the same shaft, its rotation becomes more constant because floats are not moving up down simultaneously but the motion of each one depends on the incident wave. The advantages of each case should be considered and the experience gained through use will dictate which is the most effective solution, one generator per unit or two or three units for one more powerful generator.
The required length of coast for a group of units depends on the number of units in the group and the diameter of the floats. In piers which are specially constructed for that purpose, the cages constitute four walls of recesses, while the four vertical rails attached to the walls act as guides for the floats which slide up-down in a similar way to a platform of an elevator (1/25). The front side of the recess is open towards the sea, and the corresponding vertical rail is attached on the horizontal concrete beams (1/30). FIG. 4 indicates float arrangements in three groups, one of 5 units with 3 floats in recesses and 2 outside, a second group of 15 units with 10 floats in recesses and 5 floats in their cages outside of the recesses and a third group of 9 units with floats placed without recesses. Shock absorbers are placed at the two vertical ends of the float and also at the two ends of the two beams of the metal triangle, (one towards the sea and another towards the land); in order to limit the movements of their two predetermined terminal up-down positions. In extreme situations, the front part of the recess which is open to the sea, is partly closed with special doors in order to reduce the entrance of water to a required level so the converter can operate in all weather condition.
The ground plan in FIG. 1 indicates three floats in their recesses and their basic elements. FIG. 5 indicates the function of the converter with floats in the three different positions, one in the upper, one in the middle—average sea surface level—and the third in the bottom position. All groups are housed and protected in durable and elegantly designed constructions.

Production of electric energy from sea waves


Water-soluble salts of 2-difluoromethyl-2,5-diaminopentanoic acid (DFMO) with polycations, their synthesis and uses are described.

1. Field of the Invention
The present invention relates to new salts of 2-difluoromethyl-2,5-diaminopentanoic acid (DFMO).
2. Technical Field
This patent relates to new salts of 2-difluoromethyl-2,5-diaminopentanoic acid (DFMO) with polycations such as polycationic carbohydrates (chitosan, water-soluble chitosan derivative, or a salt thereof) or a polyaminoacid, a polyamine, a polypeptide, a basic polymer, a quartinary ammonium compound or a mixture thereof, the processes for obtaining them and to therapeutic uses of these new salts. DFMO, in vitro and in vivo, is an inhibitor of ornithine decarboxylase, an enzyme that is involved in polyamine formation in organisms.
In both eukaryotic and prokaryotic cells, the decarboxylation of ornithine to putrescine, a reaction catalyzed by ornithine decarboxylase (ODC), is the first step in the biosynthesis of the polyamines known as spermidine and spermine. The polyamines, which are found in animal tissues and microorganisms, are known to play an important role in cell growth and proliferation. The onset of cell growth and proliferation is associated with a marked increase in ODC activity and an increase in the levels of putrescine and the polyamines. Although the exact mechanism of the role of the polyamines in cell growth and proliferation is not known, it appears that the polyamines may facilitate macromolecular processes such as DNA, RNA, or protein synthesis. (Tabor H, Tabor C W, Cohn M S, Hafner E W. Streptomycin resistance produces an absolute requirement for polyamines for growth on an Escherichia coli strain unable to synthesize spermidine. J Bacteriolol 1981; 147: 702-4; Mamont P S, Bohelen, P, McCann P P, Bey P, Schuber R, Tardif C. Alpha-methyl ornithine, a potent competitive inhibitor of ornithine decarboxylase, blocks proliferation of rat hepatoma cells in culture. Proc Natl Acad Sci USA 1976; 73: 1626-30.)
The association between high levels of the polyamines and rapid proliferation was discovered more than a quarter of a century ago. (Bachrach U and Weinstein A. Effect of aliphatic polyamines on growth and macromolecular syntheses in bacteria. J. Gen. Microbiol., 60: 159-165 1970.) Subsequent studies showed that activation of the enzyme ODC was important for carcinogenesis and subsequent tumor development in animal and tumor models. (Weeks C E, Hrrmann A L, Nelson F R, Slaga T J. Alpha difluoromethylornithine, an irreversible inhibitor of ornithine decarboxylase, inhibits tumor promoter-induced polyamine accumulation and carcinogenesis in mouse skin. Proc Natl Acad Sci USA 1982; 79:6028-32.)
It is currently known that increased intracellular polyamine concentrations are related to human neoplastic conditions. (Verma, A K Inhibition of tumor promotion by DL-alphadifluoromethylornithine, specific irreversible inhibitor of ornithine decarboxylase. Basic Life Sci., 52:195-204, 1990). A further example of this relationship between high polyamine concentrations and neoplasms involves colonic polyps and cancers compared to surrounding normal colon mucosa. (Hixson, L J, Garewal, H S, McGee D., Sloan D, Fennerty, M B, Sampliner R E and Gemer E W. Omithine decarboxylase and polyamines in colorectal neoplasia and adjacent mucosa. Cancer Epidemiol. Biomark. Prev. 2;369-374, 1993; Rozhin J, Wilson P S, Bull A W, and Nigro, N D. Ornithine decarboxylase activity in the rat and human colon. Cancer Res. 44: 3226-3230, 1984.)
Other groups have reported that polyamine metabolism was necessary for carcinogenesis, especially in epithelial tissues. ODC inhibitors have been found to inhibit or suppress tumor formation in models of bladder, breast, colon and skin carcinogenesis. (Verma, A K Inhibition of tumor promotion by DL-alpha-difluoromethylornithine, specific irreversible inhibitor of ornithine decarboxylase. Basic Life Sci., 52:195-204, 1990; Nigro N D, Bull A W and Boyd, M E. Inhibition of intestinal carcinogenesis in rats: effect of difluoromethylornithine for colon cancer prevention. J. Natl Cancer Inst. 77: 1309-1313, 1986; Thompson H J, and Ronan Am. Effect of DL-2-difluoromethylornithine and endocrine manipulation on the induction of mammary carcinogenesis by 1-methyl-1-nitrosourea. Carcinogenesis (Lond.), 7: 20032006, 1986.)
It is thought, however, that the mechanism of cancer prevention by ODC inhibitors such as DFMO may involve more than just inhibition of cell proliferation. Animal studies show that DFMO may act at later stages in models of chemical carcinogenesis. These stages involve the transition of non-invasive tumors to invasive cancers. (Slaga, T J. Multistage skin carcinogenesis: a useful model for the study of the chemoprevention of cancer. Acta Pharmacol. Toxicol., 55 (Suppl. 2): 107-124, 1984.)
DFMO has been studied and continues to be studied as a cancer prevention agent, especially in skin, cervical and colon cancer. (Love R R, Carbone, P P Verma, A K, Gilmore D, Carey P, Tutsch K D. Pomplun M, and Wilding G. Randomized Phase I chemoprevention dose-seeking study of alpha-difluoromethylornithine. J. Natl. Cancer Inst., 85:732-736, 1993; Nishioka K, Melgarejo A B, Lyon R R and Mitchell M F. Polyamines as biomarkers of cervical intraepithelial neoplasia. J. Cell. Biochem., 23 (Suppl.): 87-95, 1995; Mitchell M F, Tortolero-Luna G, Lee J J, Hittelman W N, Lotan R, Wharton J T, Hong, W K and Nishioka, K. Phase I dose de-escalation trial of alpha-difluoromethylornithine in patients with grade 3 cervical intraepithelial neoplasia. Clin. Cancer Res., 4:303-310, 1998; Meyskens F I, Emerson S S, Pelot D, Meshkinpour H, Shassetz R, Einspahr J, Alberts D S, and Gerner, E W. Dose de-escalation chemoprevention trial of alpha-difluoromethylornithine in patients with colon polyps. J. Natl. Cancer Inst., 86:1122-1130, 1994.)
While high doses of DFMO in humans can cause some problems with hearing (reversible upon discontinuation of DFMO), at the doses used for chemoprevention of cancer (0.50 g/m2/day) such concerns have been found to be groundless. (Meyskens F L, Gerner E, Emerson S, Pelot D, Durbin T, Doyle K and Lagerber W. A randomized double-blind placebo controlled Phase IIb trial of difluoromethylornithine for colon cancer prevention. J. Natl. Cancer Inst., 90: 1212-1218, 1998).
DFMO has also been found useful in conditions unrelated to cancer. ODC inhibitors have been associated with control of hair growth. Studies in mice have suggested that the ODC gene is an important regulatory gene for the mouse hair follicle. (Soler A P, Gilliard G, Megosh L C, O""Brien T G.J Modulation of murine hair follicle function by alterations in ornithine decarboxylase activity. Invest Dermatol 1996 May;106(5):1108-13.) The FDA, to control facial hair growth in women, has recently approved DFMO. (Current DFMO salts, when used topically, cause burning, irritation and inflammation.) DFMO may have use in controlling male facial hair growth as well and may constitute a methodology to supplant or reduce the use of razors to remove facial hair in men. New DFMO salts, which are the subject of this invention, have been shown to be less irritating, do not cause burning and inflammation when applied topically.
U.S. Pat. No. 4,330,559, May 18, 1982, Bey, et al. discloses the use of DFMO to treat benign prostatic hypertrophy. U.S. Pat. No. 4,399,151, Aug. 16, 1983, Sjoerdsma, et al. discloses the use of 2-(difluoromethyl)-2,5-diaminopentanoic acid (DFMO) for inhibiting the growth of protozoa. U.S. Pat. No. 4,405,530, Sep. 20, 1983, Gerhart, discloses the preparation of fluorinated amino-nitriles. These patents do not disclose the preparation or use of new DFMO salts of the present invention made with chitosan or polycations.
U.S. Pat. No. 4,413,141, Nov. 1, 1983 Bey, et al. discloses 2-(difluoromethyl)2,5-diaminopentanoic acid (DFMO) and the methods for the preparation and use thereof U.S. Pat. No. 4,499,072, Feb. 12, 1985, Sunkara, et al. discloses the use of DFMO as an ODC inhibitor along with interferon in treating diseases. U.S. Pat. No. 4,720,489, Jan. 19, 1988, Shander, discloses the use of DFMO as an ornithine decarboxylase inhibitor to modify hair growth. These patents do not disclose the preparation and use of new DFMO salts of the present invention made with chitosan or polycations.
U.S. Pat. No. 5,648,394 Jul. 15, 1997, Boxall, et al. discloses the use of DFMO as a topical composition for inhibiting hair growth but does not teach the use of new DFMO salts of the present invention made with chitosan or polycations. WO9814188, 1998-04-09, Love et al. teaches the use of preparations comprising a single enantiomer or defined ratio of enantiomers of alphadifluoromethylornithine (DFMO) for treating, preventing, controlling the growth of and/or reducing the risk of developing estrogen independent breast cancer or tumor and for administering DFMO alone or in combination with taxol. However, this patent does not teach the preparation and use of new DFMO salts of the present invention made with chitosan or polycations. U.S. Pat. No. 5,851,537, Dec. 22, 1998, Alberts et al. discloses the use of topical application of DFMO to prevent skin cancer but does not teach the preparation and use of new DFMO salts of the present invention made with chitosan or polycations. WO0069434, 2000-11-23, Love discloses the use of Celecoxib, a COX-2 specific non-steroidal anti-inflammatory agent, in combination with DFMO for the prevention and/or treatment of cancers. However, this patent does not teach the preparation and use of new DFMO salts of the present invention made with chitosan or polycations. U.S. Pat. No. 6,166,079, Dec. 26, 2000, Follen et al. discloses the use of DFMO for the treatment or prevention of cervical intraepithelial neoplasia. U.S. Pat. No. 6,258,845, Jul. 10, 2001, Gemer, et al. discloses the use of DFMO and sulindac combination in cancer chemoprevention. These patents do not teach the preparation and use of new DFMO salts of the present invention made with chitosan or polycations.
Administration of agents that inhibit ornithine decarboxylase would have significant utility over a wide range of disorders or conditions associated with an increase polyamine metabolism. For example, in addition to the prevention and/or treatment of different types of cancer or pre-cancer conditions, such agents would have utility in preventing and/or treating colon polyps, benign prostatic hypertrophy (BPH), or hirsutism. Such agents may also provide a means to decrease the need for daily shaving of facial hair in males.
Accordingly, there is a need in the art for agents that inhibit ODC, as well as methods related to the use of such agents to prevent and/or treat conditions associated with increased polyamine metabolism. There is also a need in the art for synthetic routes to make such agents. The present invention fulfills these needs, and provides further related advantages.
Briefly stated, the present invention discloses new DFMO salts, methods for the use thereof and synthetic methods for their preparation. These new salts of DFMO of this present invention have utility in treating or preventing a variety of conditions related to the aforementioned mechanisms of action of DFMO, namely ODC inhibition. Thus in one embodiment, a new DFMO salt is administered to a warm-blooded animal in need thereof. In yet a further embodiment, a new DFMO salt is administered to a warm blooded animal to prevent and or treat the following conditions: aging of the skin, cancer, HIV, alopecia, solar keratosis, benign prostatic hypertrophy, prostate cancer, breast cancer, cervical cancer, and other such conditions in which polyamine metabolism requires modulation. Such a salt may be administered along with any other agent to enhance its therapeutic effectiveness. Other aspects of the present invention will become evident upon reference to the following detailed description.
As mentioned above, this invention is generally directed to new water-soluble salts of DFMO. Such new DFMO salts, when administered to a warm-blooded animal in need thereof, have utility in the prevention or treatment of conditions enumerated above in warm-blooded animals, including humans.
The term xe2x80x9ctreatxe2x80x9d or xe2x80x9ctreatmentxe2x80x9d means that the symptoms associated with one or more conditions mentioned above are alleviated or reduced in severity or frequency and the term xe2x80x9cpreventxe2x80x9d means that subsequent occurrences of such symptoms are avoided or that the frequency between such occurrences is prolonged.
It has now surprisingly been found that salts of DFMO with chitosan, a polycation, have good characteristics that are such as to render them particularly suitable both for use in pharmaceutical formulations and for preparative applications.
Owing to their simple conception and low costs, the procedures described in this invention easily lend themselves to working out methods of preparation on an industrial scale.
The examples given herein below illustrate the preparation of two salts of DFMO with chitosan (as only one example of a polycation according to this invention). Only a few of the many possible embodiments that may be anticipated are shown by these examples which are intended to define, in a non-limiting sense, the scope encompassed by the invention. The examples illustrate two possible synthetic routes according to the invention as well as the complete absence of side effects when a 20% cream is applied topically to the forearm of healthy volunteers.
These examples are given to illustrate the present invention, but not by way of limitation. Accordingly, the scope of this invention should be determined not by the embodiments illustrated, but rather by the appended claims and their legal equivalents.


A method and apparatus for network management is described. In one embodiment, a method comprises collecting performance data having accompanying meta data including information defining the performance management data and information indicating operations to be performed on the performance management data, and generating output data for display using collected performance management data according to the information indicating the operations to be performed on the performance management data.

The present invention pertains to the field of network management. More particularly, this invention pertains to the field of interfacing with network management.
Networks are used to interconnect multiple devices, such as computing devices, and allow the communication of information between the various interconnected devices. Many organizations rely on networks to communicate information between different individuals, departments, work groups, and geographic locations. In many organizations, a network is an important resource that must operate efficiently. For example, networks are used to communicate electronic mail (e-mail), share information between individuals, and provide access to shared resources, such as printers, servers, and databases. A network failure or inefficient operation may significantly affect the ability of certain individuals or groups to perform their required functions.
A typical network contains multiple interconnected devices, including computers, servers, printers, and various other network communication devices such as routers, bridges, switches, and hubs. The multiple devices in a network are interconnected with multiple communication links that allow the various network devices to communicate with one another. If a particular network device or network communication link fails, multiple devices, or the entire network, may be affected.
Network management is the process of managing the various network devices and network communication links to provide the necessary network services to the users of the network. Typical network management systems collect information regarding the operation and performance of the network and analyze the collected information to detect problems in the network. For example, a high network utilization or a high network response time may indicate that the network (or a particular device or link in the network) is approaching an overloaded condition. In an overloaded condition, network devices may be unable to communicate at a reasonable speed, thereby reducing the usefulness of the network. In this situation, it is important to identify the network problem and the source of the problem such that the proper network operation can be restored.
The operations performed by the network management system are often controlled via software on one or more computer systems. Typically, in the prior art, a determination is first made to determine what the application is and then software is created to control how to administer it, how to control it, how to configure it, and how to display it. The result is software that is very specific to the types of data that is being collected, stored, analyzed and displayed. Because of this, there is new code written for each application and stored for use in the system. As developing such software is time consuming and expensive, it would be advantageous to reduce the amount of software development in network management systems.
Furthermore, typical computer network management systems collecting data from components within a network, these network management systems usually collect typical infrastructure information only, such as server response time, and network parameters such as packets transmitted, packets lost, etc. They do not collect specific business-oriented data useful in commercial applications. In fact, management or business-oriented data is usually neglected by current network management system. For example, a typical network management system does not keep track of the number of tickets sold in an airline""s web site, even though the statistics on the number of tickets sold would be very useful to an airline using the network management system. In this situation, the company usually has its own network management staff to generate a script-based program to collect this particular piece of information, in addition to the data already collected by the system installed. Although the script-based program is relatively simple to generate, additional effort is required to integrate the customized data collected (e.g., the number of tickets sold in the airline""s web site) with the typical data collected by the network management system. Even more effort and time is required to analyze these different types of data in order to maintain the network and to troubleshoot.
In one embodiment, a method comprises collecting performance data having accompanying meta data including information defining the performance management data and information indicating operations to be performed on the performance management data, and generating output data for display using collected performance management data according to the information indicating the operations to be performed on the performance management data.

Interfacing external metrics into a performance management system


A motor vehicle roof with a fixed roof structure having a roof opening, two successive adjustable covers for closing and at least partially clearing the roof opening. At least one of the covers is selectively movable longitudinally out of its closed position into an open position and both of the covers are selectively pivotable out of their closed positions into a ventilation position.

1. Field of the Invention
The present invention is directed to a motor vehicle roof including a fixed roof structure having front and rear roof openings, two selectively adjustable covers for closing a respective roof opening, whereby at least one of the covers is selectively movable longitudinally from a closed position into an open position to at least partially clear a respective roof opening, and whereby the covers are pivotable out of the closed position into a ventilation position. The invention, furthermore, relates to a headliner arrangement for a motor vehicle roof with a roof opening which is made in the fixed roof structure and with two successive adjustable covers for closing and partially clearing the roof opening, and the front headliner unit can be pushed out of the covering position which is assigned to the front cover to the rear into the open position, and the rear headliner unit can be pushed out of the covering position assigned to the rear cover, forward into the open position.
2. Description of the Prior Art
European Patent Publication EP 0 447 781 A2 describes a sliding and lifting roof with two covers which are located in succession in a closed position which closes the roof opening. The front cover can be raised at its rear edge from the closed position into a ventilation position. When the front cover is raised into the ventilation position, the displacement means forcibly lowers the front edge of the rear cover. In the raised ventilation position of the front cover, it can be shifted to the rear to over the rear cover, or the rear cover can be pushed under the front cover in order to clear the front or the rear section of the roof opening.
With known headliner arrangements of the type the invention is directed toward, two comparatively large-area headliner elements are guided on respective guide rails which are located with a vertical offset relative to one another under the fixed roof structure so that they can be stowed at the same time on top of one another under the middle part of the roof. However, the free head space for vehicle passengers is reduced by the guide rail which has been offset down.
The object of the invention is to devise the initially mentioned motor vehicle roof in which optimized ventilation of the motor vehicle can be achieved by different cover positions.
Another object of the invention is to devise a headliner for a motor vehicle roof of the initially mentioned type which can be stowed under the roof in its open position with little space requirement.
These and other objects may be achieved in accordance with the present invention in the initially mentioned type of motor vehicle roof in that the front cover and the rear cover can be raised with their respective rear edges about their front edges into their ventilation positions. The rear edges can be raised by pivoting the cover about its front edge or about a transverse axis which runs in the continuing area about the front edge of the cover. Accordingly, two sliding and lifting roofs are combined, and the rear sliding and lifting roof or the rear cover can be moved forward to under the front cover by a guide mechanism from its closed position.
The objects may also be achieved in the initially mentioned type of motor vehicle roof in accordance with the present invention also in that the front cover can be lowered about its rear edge into its ventilation position and the rear cover can be raised about its front edge into its ventilation position. The front, lowerable cover, as a result of the lowering of its front edge, is also called the xe2x80x9cfront ventxe2x80x9d. By way of the lowered front edge on the front cover and the raised rear edge of the rear cover two ventilation openings which are distant from one another are made available with improved ventilation action for the entire motor vehicle interior.
Furthermore, the objects may be achieved in accordance with the present invention in the initially mentioned motor vehicle roof in that the front cover can be pivoted about its front edge into its ventilation position and the rear cover can be lowered about its rear edge into its ventilation position.
Finally, the objects of the invention may be achieved such that the front cover and the rear cover can be lowered on their respective front edges about their respective rear edges into their ventilation positions. In addition, in a preferred embodiment, the motor vehicle roof includes a pivotable wind deflector in front of the front cover, the wind deflector being pivotable so that a draft can be produced for ventilating the interior of the motor vehicle, and especially for the front cover which can be lowered on its front edge, a clearly larger ventilation opening can be set when the pivoted-out wind deflector also clears an additional opening.
The objects may also be achieved with respect to the aforementioned headliner in that the two headliner units are guided roughly in a common plane near the roof out of their cover positions in the direction to their open positions and that at least one of the two headliner units in the longitudinal direction is divided into at least two headliner elements which can be displaced or pivoted relative to one another, and while it is being pushed to its open position, it is guided from its arrangement near the roof to under the other headliner unit. The division of the large-area headliner unit into at least two or even more headliner elements which are shorter in the longitudinal direction makes the headliner unit flexible about one or more transverse axes such that it can be moved into a stowed position and can be deposited therein, and the guides to the stowage position can be located near the roof. In this way, the head space for the vehicle passengers is not unduly limited. The headliner unit can have individual, separate elements which can be flexibly or pivotably joined to one another, or alternatively, it can be made in one piece with sections divided in the longitudinal direction with varied bending flexibility in order, for example, to be able to follow a guideway which is bent in a S-shape.
Preferably, a headliner unit is movably supported on a guide which essentially follows the roof contour and which extends from the assigned cover to the middle part of the headliner, and the other headliner unit is movably guided on a guide which runs in the area of the middle part of the headliner underneath the other guide. If the two headliner units can be moved independently of one another, according to the requirements of the vehicle passengers, then only one of the headliner elements can be partially or completely closed.

Motor vehicle roof with two covers and a headliner for one such motor vehicle roof

Webasto Vehicle Systems International GmbH


A ballistic projectile velocity measurement apparatus including two screens spaced apart at a known fixed distance for providing time measurement start and stop signals indicative of the passage of a ballistic projectile through a light curtain formed by contiguous focused light beams from plural infrared light sources which causes a perturbation or fluctuation in the light intensity level received by one or more photo-optic sensors to calculate the speed or velocity of the ballistic projectile. A calculation and display unit for receiving the time measurement signals, calculating the speed or velocity of the ballistic projectile and storing and displaying the sensed and calculated information is connected to the screens and controlled by keyboard command.

This invention relates to an apparatus utilizing infrared photo detection and associated electronic circuitry to determine the respective times when a ballistic projectile traverses through a focused infrared light curtain to calculate instantaneous speed, and thus, ballistic velocity.
In measuring ballistic projectile velocity, it has been common practice to use a pair of broad-band photodetectors spaced apart at a fixed known distance to produce, in turn, a signal to a common timing circuit at the point in time that a projectile interrupts the light detected by the photodetector indicating the projectile has just passed over each detector. The interval between each of the signals from the photodetectors indicating that a projectile has been detected and the known distance between the pair of photodetectors are used to compute the velocity of the ballistic projectile as it traversed the course, i.e. the distance, between the photodetector assemblies.
The assemblies housing the photodetectors, which are typically photo diodes or phototransistors, normally operate by having these receiving elements placed so that they can receive steady broad-band illumination from a constant light source such as the sun, specialty high intensity incandescent bulbs, or other broad-band light source. The photodetector assemblies are typically called xe2x80x9cscreenxe2x80x9d in the ballistic projectile velocity measurement field for the reason that such assemblies have replaced earlier physical conducting grids or screens which recorded the passage of a projectile. Earlier screens were designed to utilize either incandescent light sources or ambient light from environmental sources, i.e. the sun. Screens utilizing ambient light from the sky required an optical slit, or other masking device, to restrict extraneous sources of light from being detected by the photodetectors.
With early photodetector assemblies, one typical problem encountered was that the illumination received by the photodetection receivers was not constant because of varying photoemission levels from the incandescent lamp or lamps, a varying amount of dust or other particles in the light transmission path between the source and the receiver, aging of the incandescent lamp filament, varying distances from the light source and the receiver, and varying atmosphere conditions and angles of the light source, i.e. the sun, in the case of sky screens. Particularly with regard to sky screens, the photosensitive receivers view only a segment of unobstructed sky through an optical slit which created a problem with the illumination level from the light source. On clear days, the illumination level was less than on hazy or partially obscured (cloudy) days and, for that reason, in order for a sky screen to properly operate under available light conditions, the light needed to be diffused, rather than be received directly from the source. Thus, while the optical slit created a partial focusing of the light, the diffuser element dispersed the direct light over a broader expanse, which also reduced potential problems from reflected light. Neither light source, incandescent or ambient, produced a constant, fixed level illumination source of light from which the photodetection receivers could detect the passage of a projectile because of the number of variables existing in the illumination source and from environmental conditions.
One environmental problem referenced above, i.e. reflected light, can cause a number of different types of misreadings by the photodetection receiver. When using ambient light from the sun, directed through an optical view slit (but without a diffuser), it was possible that the photodetector would respond because the circuit associated with that receiver was designed to detect any perturbation in the light level about the ambient level, regardless of the direction of that perturbation, lighter or darker. This is to say that reflected light from the projectile can be less than, approximately equal to or greater than the amount of diffused light blocked by that projectile. If the reflected light is significantly greater than or significantly less than the amount of diffused light blocked by the projectile, the photodetection receiver would react as described above. In the case in which the reflected light is approximately equal to the amount of the diffused light which reaches the photosensitive element in the absence of a projectile, the receiver sees no significant change in the light level even though the projectile is passing between the light source and the receiver. Thus, a shadow, which would be expected to fall across the photosensitive element or elements, is essentially obliterated by the reflected light. Due to the cancellation of the shadow, which occurs earlier then the calculation within the apparatus where a change in light level is converted to an electrical signal and a time tag is placed on the signal, there is no way to recover the lost information by using any substituted electrical signal processing technique.
Attempts to overcome the problems of insufficient light to cause a shadow to interrupt the light being detected by the photodetection receiver and from reflected light which causes inaccurate and/or incorrect detection have required apparatus measuring projectile velocity to include focusing arrays to direct light, which would otherwise disperse, to not disperse as quickly so that a greater level of illumination is presented to the photodetection receiver when the light source is ambient environmental light, i.e. the sun. The problem and the cure are described in U.S. Pat. No. 4,239,962 [Oehler] for xe2x80x9cSun Shield and Light Diffuserxe2x80x9d. This patent describes a sun shield for redirecting ambient light away from the photodetector/sensor so that only a small amount enters through an opening directly above the sensor and is then diffused to flood the area of the sensor with a light having substantially the same light intensity so that errors in sensing the passage of a projectile through low level light intensity and reflected xe2x80x9cshadowsxe2x80x9d are substantially eliminated.
While it appears that the Oehler patent is the final word on using incandescent light or sunlight as the source of illumination for photodetection sensors or receivers, a different type of light, one which is not broad-band, was attempted. In U.S. Pat. No. 4,180,726 [De""Crescent] for xe2x80x9cA System for Measuring Characteristics of an Object in Motionxe2x80x9d, the apparatus described uses pulsed infrared light beams to detect the passage of an object between the light beam source and the detector. Relatively low speed motion of balls involved in sports, sports apparatus swings, etc., are discussed but there is no mention of high speed or high velocity projectile measurement. This is largely due to the pulsing of the infrared beam which may be at the precise instant that the projectile traverses the path of the beam, when the beam is not present, and the detector will be unable to sense an interruption in the light beam.
Therefore, it is an object of the present invention to provide a ballistic projectile velocity measuring apparatus which has a more stable and constant light source for providing sufficient light intensity across the entire area within the screen or frame in order to be able to unfailingly detect the passage or traversal of the projectile through the screen as it impinges upon or traverses the light beam.
It is also a further object of the present invention to provide a contiguous series of light sources within the screen or frame to produce a special wavelength light beam emanating from above and traversing the internal area of the screen or frame downward to a photodetector/sensor array with the lightwave length selected so that the possibility of reflected light causing a sensing error is minimized.
It is still a further object of the present invention, in order to provide a more uniform illumination throughout the entire area within the screen of frame, to create a light curtain formed by multiple light sources of the special wavelength and the photodetector array which permits the detection of the passage or traversal of the projectile at any point through the light curtain.
It is also an object of the present invention to provide an apparatus to be linked to the screens or frames to receive the sensor information, time mark or tag that information, calculate the speed or velocity of the ballistic projectile, store such speed or velocity of the ballistic projectile in non-volatile memory and be able to control a display and recall all data and information regarding the time sensor data for the ballistic projectiles.
It is still a further object of the present invention to be able to provide a printed report of the time sensor data of the ballistic projectiles and to transfer information from the display and calculation apparatus to a multi-purpose computer and/or print reports of the time sensor data.
Other objects will appear hereinafter.
A ballistic projectile velocity measurement apparatus is described which includes two screens which are spaced apart at a known or fixed distance for providing time measurement start and stop signals indicative of the passage of a ballistic projectile through a light curtain formed by contiguous focused light beams from plural infrared light sources. The passage of a ballistic projectile through the light curtain will cause a perturbation or fluctuation in the light intensity level received by one or more photo-optic sensors. The detection and time measurement is used to calculate the speed or velocity of the ballistic projectile. A calculation and display unit for receiving the time measurement signals, calculating the speed or velocity of the ballistic projectile and storing and displaying the sensed and calculated information is connected to the screens and controlled by keyboard command is also described.
The invention may be best described as a measurement and calculation apparatus for measuring the time a ballistic projectile enters and exits a prescribed course, passing through preselected zones along the course. The apparatus includes first and second screens having sidewalls angled outward from a base and capped by a light shield. These screens are arranged in a sequential array downrange from a firearm shooting position and are positioned laterally across the intended shot line of a ballistic projectile. Infra-red illumination means mounted below the light shield produce a light beam or curtain extending downward into and across substantially the entire area within each screen impinging upon an elongated rectangular slit in the top side each base. A plurality of photodetector sensors contained in each base below the rectangular slit are responsive to perturbations in the infra-red light made by the passage of a ballistic projectile through the light beam or curtain and, following detection of the light perturbation, generate timing signals indicative of the passage of the ballistic projectile. A calculation and display means is responsive to the timing signals from the photodetector sensors in the first and second screens for measuring the time interval between the respective passages of a ballistic projectile through the light curtain or beam in each of the first and second screens for calculating a speed corresponding to the measured time and the distance between the first and second screens for each ballistic projectile so measured. The calculation and display means also stores and displays the calculated speed associated with each ballistic projectile in turn.
The infra-red illumination means is comprised of a plurality of individual light sources capable of producing light in the infra-red wavelengths mounted across the lateral dimension of the screen immediately below the sun shield with an associated lens juxtaposed opposite each one of the plurality of light sources for focusing the produced light into convergent beams which overlap one another and form said light curtain. The photodetector sensor means is comprised of a focusing lens to receive the light passing through the slit in the top of the base which causes that portion of the infra-red light curtain passing through the slit to converge and be passed onto a photosensor capable of detecting perturbations in the infra-red light. Additionally, a diverging lens may be positioned between the focusing lens and the photosensor to cause the light beam to slightly diverge to encompass the lens of the photosensor.
The calculation and display means, which is responsive to said timing signals from the photodetector sensor means in the first and second screens, is also capable of causing the calculated speed to be aurally expressed by a voice modulator. Further, the calculation and display means can receive commands from an associated keyboard, link with a personal computer through a communications port, and transfer data to a printer through an infra-red port for printing reports containing the stored information.

Infrared photodetector apparatus for measuring projectile velocity


A video system is disclosed that processes OSD images and displays the OSD images on a display. At least some of the OSD images are represented by data sets that do not include a color palette. Each OSD data set includes a header comprising multiple bits of status and control information. One of the control bits indicates whether the OSD data set includes a color palette. Preferably that control bit is set to indicate no color palette in present and cleared to indicate the inclusion of a color palette in the OSD data set. By not including a color palette in an OSD data set, the corresponding OSD image can be represented with a smaller data set and can be transferred across a bus with a smaller bandwidth. If the control bit is set, indicating the absence of a color palette in the OSD data set, a color palette included in another OSD data set is used instead to draw the desired OSD image.

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1. Field of the Invention
The present invention generally relates to video display systems. More particularly, the present invention relates to on-screen display images generated by video display systems. More particularly still, the invention relates to an improved data format for on-screen displays to reduce bandwidth in a video system.
2. Background of the Invention
The consumer electronics industry has experienced a dramatic explosion in product development over the last 20 years. This explosion has been fueled by consumer demand coupled with significant advances in semiconductor technology that have lead to lower cost semiconductor devices incorporating significantly more functionality than previously possible. For example, a hand-held calculator from 20 years ago provided the ability to perform rudimentary mathematical operations. Today, a hand-held device can provide much of the functionality of a desktop computer system.
Significant advances have also been made with respect to video equipment, such as televisions, videocassette recorders (VCR""s), and the video and graphics subsystems in personal computers. This sophistication of these types of equipment has increased to a level where it has been necessary for the equipment manufacturers to devise new types of user interfaces to insure that the equipment remains easy to use. Rather than providing buttons, switches, and knobs on the front panel of such equipment, the manufacturers instead often design the equipment to be operated by xe2x80x9con-screen displaysxe2x80x9d (OSD""s). An OSD is a window that xe2x80x9cpops upxe2x80x9d on the television or computer display and provides a control interface for the user. For example, many VCR""s are programmed by pressing a xe2x80x9cmenuxe2x80x9d button on the remote control. In response, an OSD pops up on the television screen and provides menu choices to permit the user to program the VCR. The user then can use the remote control to scroll through the various OSD menu choices and select the desired choices for programming the VCR. OSD""s are also used in conjunction with digital video disk (DVD) players, personal computers, and other types of equipment.
An OSD represents an image that is drawn on a television or computer screen. Such screens typically are comprised of a plurality of rows and columns of xe2x80x9cpixels.xe2x80x9d A typical television screen comprises a grid of pixels in accordance with one of at least two industry standard formats. In the NTSC standard, each frame of video includes 720 columns of pixels with each column including 480 pixels (720xc3x97480). The PAL standard includes a pixel grid of 720xc3x97576 pixels. Computer screens typically have a higher resolution. A full screen OSD is typically divided into several regions transparent to the user. An OSD image typically covers only a portion of the screen and thus includes less than the total number of pixels available on the screen.
Recently, digital video disk (DVD) systems and have become available as an alternative to VCR""s. A digital video disk resembles a CD-ROM disk and can store an entire movie including both video and audio information as well as other information. DVD systems can be connected to a television or incorporated into a computer system. The present invention relates to an improved format for representing OSD images. The principles of the invention are applicable with respect to any video equipment that generates OSD""s. For simplicity in explaining the preferred embodiments of the invention, however, this disclosure focuses on OSD images in the context of DVD systems.
A DVD system typically includes a microcontroller for controlling the drive, memory for storing video data and other information, a decoder for decoding video, audio data stored in a predefined coded format such as in Moving Pictures Experts Group (MPEG), and other components. The OSD information is stored in memory generally according to the format shown in FIG. 1 which illustrates OSD information for three different on-screen displaysxe2x80x94OSD 1, OSD 2, and OSD 3. Each OSD data set itself comprises three types of data. The header data includes information regarding the location of the associated OSD image on the television or computer screen, as well as other needed information for drawing the OSD image. The color palette includes digital representations of one or more colors that can be used to draw each pixel in the OSD image. The pixel data includes a value associated with each OSD pixel that specifies which color from the color palette is to be applied by the audio and video decoder to that pixel. Thus, in conventional video systems every OSD data set includes a header, a color palette and pixel data
Each OSD data set requires a finite amount of memory for storage. As more colors are added to the color palette, the color palette requires more memory for storing the additional colors. Similarly, as the size of the OSD image itself becomes larger and thus encompasses more screen pixels, the amount of pixel data increases thus requiring more memory for storage. For the video decoder to display an OSD image on the display, the desired OSD data set must be transferred from memory where it is stored to the decoder. The transfer of an OSD data set from memory to the decoder takes a finite amount of time which disadvantageously increases for larger OSD data sets. Further, images on a computer or television monitor are re-drawn many times each second (generally 30 times per second). The rate at which the screen is re-drawn is sufficiently fast to be imperceptible to the human eye. Thus, the image looks constant (i.e., does not flicker) on the screen. Because the OSD may change at any point in time (e.g., removed from the screen altogether or changed based on input from the user), it is generally necessary to re-copy the entire OSD data set from memory to the video decoder every time the screen is re-drawn. Re-copying the entire OSD data set is also required because most video decoders do not include enough internal memory to store all of the OSD data sets at one time.
The memory in which OSD information is stored is also shared by other components in the DVD system. For example, the memory is also used to store information relevant to the decoding and display processes as well as general configuration information. Thus, a xe2x80x9cbottleneckxe2x80x9d may occur as multiple devices compete for access to memory. Generally, data is transferred from one device in an electronic system to another device across a collection of digital signal lines collectively referred to as a xe2x80x9cbus.xe2x80x9d Typically, a single bus may interconnect numerous electronic components. Most bus communication protocols only permit one transaction (e.g., data transfer) to run at a time on the bus. Other components connected to the bus also desiring to use the bus to execute a transaction must wait until the prior data transaction completes.
The maximum rate at which data can be transferred across a bus (generally referred to as the xe2x80x9cbandwidthxe2x80x9d of the bus) is determined by the particular types of components connected to the bus as well as the communication protocol implemented by the bus. Because the complete OSD data set must be transferred from memory to the audio and video decoder across a bus many times each second and other components in the DVD system may also need access to the bus, it may be difficult for the video system to timely accomplish all that is required given the bandwidth limitation of the bus.
One solution to this problem might be to develop electronic components that operate at faster speeds than previously possible. As such, the bandwidth of the bus used transfer the OSD data could be increased. Although this approach should not be neglected, it is generally a costly approach that requires significant development and testing time and resources. Accordingly, it would be desirable to be able to transfer OSD data across a bus in less time than previously possible given an existing data bus transfer rate.
The deficiencies noted above are solved in large part by a video system that processes OSD data sets, at least some of which do not include a color palette. In accordance with the preferred embodiment, each OSD data set includes a header comprising multiple bits of status and control information. One of the control bits is a BITMAP ONLY (BMP ONLY) bit that indicates whether the OSD data set includes a color palette. Preferably the BMP ONLY bit is set to indicate no color palette in present and cleared to indicate the inclusion of a palette in the corresponding OSD data set. By not including a color palette in an OSD data set, the OSD image can be represented with a smaller data set, and the bus bandwidth problem is alleviated.
In one embodiment of the invention if the BMP ONLY bit is set, indicating the absence of a color palette in the corresponding OSD data set, a color palette included in another OSD data set is used instead to draw the desired OSD image. Accordingly, bit map data from one OSD data set specifies which colors are to be used from a color palette in another OSD data set. This embodiment is particularly beneficial when multiple OSD""s are to be displayed all using the same colors. Alternatively, a default color palette can be used if desired.
The video system implementing the invention preferably represents the processing circuitry in a digital video disk (DVD) drive, although the invention can be implemented in other types of video equipment as well. The video system preferably includes an audio/video decoder connected to memory and other devices. The audio/video decoder includes a microcontroller coupled to various functional units including a memory interface, a video decoder and a video interface over a bus.
OSD data sets and MPEG encoded video data stored in memory are transferred through the memory interface into the audio/video decoder. The video decoder decodes the encoded data and filters included in the video interface further process the decoded video data. The video interface also includes an OSD mixer that mixes OSD data with the processed video data. The OSD mixer examines the BMP ONLY bit, preferably included in a header portion of each OSD data set, and if the BMP ONLY bit is configured to indicate the absence of a color palette in the data set, the OSD mixer uses a color palette from another data set or uses a default color palette.
The invention permits OSD images to be represented with fewer bytes than previously possible, thus alleviating the bandwidth problem of data transfers on a bus in a video system. These and other benefits and advantages will become apparent after reading the following disclosure in conjunction with the drawings.

On-screen display format reduces memory bandwidth for on-screen display systems