An apparatus adapted for coupling between an attendant positioned either behind or in front of a patient on an exercise assembly such as a treadmill for rehabilitation of a functionally impaired leg of the patient such as one suffering from paralysis. The apparatus comprises a leg appliance secured to a patpatient""sg, with a leg bracket adjacent to the knee. A leg brace secured to an attendant""s leg also includes a bracket adjacent to the attattendant""see. At least one connecting member provides coupling from the leg bracket to the bracket of the leg brace to transmit motion from an attendant""s leg to a patient""s leg using forces acting from the leg brace to the leg appliance through the connecting member. An ankle appliance having an upper extension and a lower extension proximate the ankle is attached to a patient""s foot and an ankle brace is similarly attached to an attendant""s foot. The ankle brace has a brace upper extension and a brace lower extension adjacent the ankle of an attendant with the brace upper extension coupled by an upper ankle link to the upper extension of the patient""s ankle appliance, while the brace lower extension is coupled by a lower ankle link to the lower extension of the ankle appliance. Each of the upper link and the lower link are adapted to create movement of a patient""s foot corresponding to movement of a foot of an attendant during walking. Further coupled to the ankle brace is an offset link for transferring side-to-side motions. The coordinated leg and ankle movement allows a patient""s paralysis damaged leg to duplicate the walking motion of an attendant""s leg.

1. Technical Field
The present invention generally relates to equipment used during rehabilitation of spinal and otherwise injured patients. More specifically, the present invention relates to an apparatus for assisting a patient to perform walking motion by connection of the apparatus between the legs of an injured patient and the legs of an attendant.
2. Background Information
Rehabilitation for victims of leg paralysis resulting from spinal cord injury requires using equipment that gives a paralyzed patient the opportunity to revitalize dormant muscles during relatively normal physical activity. Physical therapy for these patients has begun employing exercise assemblies such as treadmills that are normally associated with health and fitness clubs and the like.
In one application, a patient wears a body harness that supports the pelvic area and the upper torso while using a specially adapted treadmill. A strap extending from each shoulder to above the head of the patient attaches to an overhead support bar that is part of a support frame. A cable and pulley arrangement is activated to draw the shoulder straps up towards the support bar. This apparatus exerts an upwardly directed force on the patient in magnitude up to and including the point at which all weight has been counteracted and therefore removed from the patient""s legs. Positional adjustment of the support frame allows the patient""s feet to rest on the flat surface of the treadmill.
Once the treadmill begins to move the patient""s feet contacting the flat surface are drawn along by the movement. In order to perform a walking motion, the patient traditionally has required assistance from one or more attendants. When performing such a therapeutic procedure, each attendant occupied a position by the side of the treadmill from which they could reach, lift and move the patient""s legs in a motion that mimicked the walking process. A paraplegic required two attendants occupying positions on both sides of the treadmill in order to lift and move the patient""s legs through the correct actions for walking. Alternatively, each attendant placed a foot of the patient in a forward position ahead of the patient""s body. Normal, linear movement of the treadmill then displaced the foot to a position behind the patient. Completion of each attendant-assisted movement represented one stride for the patient. When a striding foot reached its rearmost position, the attendant on that side of the patient again lifted the foot from the flat surface of the treadmill and pulled it forward back to the starting position readied to allow the treadmill to effect another stride. The process of assisted walking of the suspended patient would continue giving the patient the opportunity to attempt to xe2x80x9clearnxe2x80x9d the waking process over again, while simultaneously strengthening their legs from the effort they are able to contribute during the therapy session.
The use of this technique for rehabilitation by reintroducing spinal injury sufferers to the familiar motion and pleasure of walking has been encouraging in terms of its results. For example, a hemiplegic, i.e., one who retains control over one leg, may perform a walking motion with assistance from only one attendant. The attendant repositions the injured leg while the patient still controls and moves his or her functioning leg. As indicated above, a paraplegic requires two attendants, i.e., one for each leg. Further, a quadriplegic requires even additional attendants for steadying the suspended body while the walking therapy is in progress.
A scarcity of skilled attendants limits the number of patients who may benefit from this type of rehabilitating treatment. This has led to attempts to develop mechanical devices that may assist with the walking process in the absence of an attendant.
One such device is a jointed leg brace that includes computer controlled actuators for moving sections of the brace in a way that simulates the gait of a walker. The brace is a complicated structure that must be strapped to a patient""s hip, as well as outside the patient""s leg in three locationsxe2x80x94at the thigh, just above the calf and at the ankle. One or two braces may be used, depending upon the patient""s condition. As before, the patient wears a harness for suspension by a frame with his or her feet resting on the flat surface of a treadmill. As the treadmill moves, the computer controlled brace performs strides by appropriately lifting and placing the patient""s legs relative to the moving treadmill.
This use of computer controlled equipment presents at least two potential disadvantages. Firstly, there is the associated cost, which includes an expensive, computer assisted mechanical structure and its associated maintenance. Such a mechanical structure may be at least as expensive as the use of multiple rehabilitation attendants. Secondly, there is the possibility of computer or equipment malfunction that, in extreme cases, could lead to further injury of an unattended patient.
In view of the above described deficiencies associated with the use of known designs for assisted walking rehabilitation equipment and procedures, the present invention has been developed in order to alleviate these drawbacks and provide further benefits to the user. These enhancements and benefits are described in greater detail herein below with respect to several alternative embodiments of the present invention.
The present invention in its several disclosed embodiments alleviates the drawbacks described above with respect to conventionally designed rehabilitation equipment. It incorporates several additionally beneficial features that simplify therapy procedures and lower costs by reducing attendant-to-patient ratio.
Rehabilitation procedures according to the present invention require the use of equipment and apparatus to assist a patient paralyzed by spinal or other trauma, such as strokes or other illnesses, to perform a walking motion. An attendant supervises and works with the patient in exercise activities related to walking. Equipment used during supervised exercise includes a body harness worn by the patient and a treadmill. The body harness attaches to an overhead support that bears an adjustable portion of the weight of the patient while allowing contact between the patient""s feet and the movable belt of the treadmill. A supervising attendant takes a position on the treadmill either in front of or behind the patient.
Before exercise begins, connection is made between the healthy legs of the attendant and the injured legs of the patient using rehabilitation apparatus according to the present invention. The rehabilitation apparatus includes a leg appliance and ankle appliance worn by the attendant and patient, with separate linkage between the leg appliances and the ankle appliances. A single piece of apparatus comprises two leg appliances adapted for interconnection between the attendant and patient, as well as two ankle appliances also adapted for interconnection between the patient and attendant. One or two pieces of rehabilitation apparatus may be used depending on the need for treatment to one or both of the patient""s legs. For example, an injured left leg would require connection of the left leg of the patient to the left leg of the attendant. A paraplegic patient would require both legs to be connected to the legs of the attendant.
After positioning and connecting the rehabilitation apparatus between the patient and attendant, the treadmill may be energized causing the belt to move. As the belt slowly moves, the attendant begins to walk. The rehabilitation apparatus transmits the walking motions of the attendant through the connected leg appliances and linked ankle appliances to the patient""s legs, depending on which are connected. Each step taken by the attendant at a position walking behind or in front of the patient causes stepping motion to be induced in and performed by the patient under the motivation and control of the rehabilitation apparatus. While an attendant""s healthy legs lift and reposition a patient""s injured legs, the attendant positioned behind the patient may also reach forward to the patient above the waist to assist with stability and weight transfer as the patient attempts to re-develop their ability to walk. The positioning of the attendant and use of the rehabilitation apparatus provide a much improved approach to increasing the confidence and desire of a patient to regain their ability to walk unaided.
More particularly, the present invention provides an apparatus adapted for coupling between an able-bodied attendant positioned behind a patient for rehabilitation of a leg damaged by paralysis. The apparatus comprises a leg appliance secured to a patient""s shin, with a leg bracket adjacent to the patient""s knee. A leg appliance or brace secured to an attendant""s shin also includes a bracket adjacent to the knee. At least one connecting rod provides coupling from the leg bracket to the bracket of the leg brace to transmit motion from an attendant""s leg to a patient""s leg using forces acting from the leg brace to the leg appliance through the connecting rod.
An ankle appliance having an upper extension and a lower extension proximate the ankle is attached to a patient""s foot and an ankle brace is similarly attached to an attendant""s foot. The ankle brace has a brace upper extension and a brace lower extension adjacent the ankle of the attendant with the brace upper extension coupled by an upper ankle link to the upper extension of the patient""s ankle appliance, while the brace lower extension is coupled by a lower ankle link to the lower extension of the ankle appliance. An offset link is connected to the attendant""s or patient""s ankle brace. This link extends rearwardly, where it slidably engages with a stationary support. This arrangement assists the attendant in transferring side-to-side foot motions to the patient without undue twisting or stressing to the ankle and leg of the attendant. Each of the upper link and the lower link are adapted to create movement of a patient""s foot corresponding to movement of a foot of an attendant during walking whereby coordinated leg and ankle movement allows a patient""s paralysis damaged leg to duplicate the walking motion of an able-bodied attendant""s leg. It should be appreciated that the apparatus not only provides for the proper leg extension and foot placement for the walking action, but also utilizes appropriate parallel connections and link for communicating the tilting and side-to-side motions, respectively, of the foot as it moves through a step.
The beneficial effects described above apply generally to the exemplary devices and mechanisms disclosed herein of the rehabilitation apparatus for spinally injured patients. The specific structures through which these benefits are delivered will be described in detail herein below.

Therapeutic and rehabilitation apparatus


A chromatographic process for separating racemic mixtures using a set of chiral stationary phases based on yohimbine and its derivatives has been developed. In particular, the hydroxyl functionality of yohimbine and its analogs is covalently bonded via a urethane linkage to a polymethylenesilyl chain attached to the bound hydroxyl groups of a refractory inorganic oxide by Sixe2x80x94O bonds. The resulting chiral stationary phases have multiple chiral recognition sites and can be used with a broad spectrum of materials as eluents without leaching.

Ever since Pasteur discovered the property of optical activity displayed by chiral compounds, the resolution of racemic mixtures into their enantiomeric components has posed a challenge. Substantial progress in separating enantiomeric pairs has been achieved since Pasteur""s laborious hand separation of the enantiomeric crystals of racemic sodium ammonium tartrate, yet methods of resolution, and the materials used therefor, remain a formidable obstacle to commercial production of optically active organic substances.
A traditional method of resolution comprises reacting a racemic mixture with a second optically active substance to form a pair of diastereomeric derivatives. Such derivatives generally have different physical properties which permit their separation by conventional means. For example, fractional crystallization often permits substantial separation to afford at least one of the diastereomers in a pure state, or largely so. An appropriate chemical transformation then converts the purified derivative, which was formed initially solely to prepare a diastereomeric pair, into one enantiomer of the originally racemic compound. This traditional method is exemplified by the reaction of naturally occurring optically active alkaloids, for example, brucine, with racemic acids to form diastereomeric salts, with release of an optically active organic acid from a purified diastereomer upon acidification of the latter.
Such traditional methods suffer from many limitations. Generally, only one of the enantiomeric pairs can be obtained, so yields are necessarily less than 50%. The separation of the material so obtained usually is incomplete, leading to materials with enhanced rather than complete optical purity. The optically active materials used to form the diastereomers frequently are expensive and quite toxicxe2x80x94the alkaloids as a class are good examplesxe2x80x94and are only partially recoverable. Regeneration of optically active material from its derivative may itself cause racemization of the desired compound, leading to diminution of optical purity. For example if optically active benzyl alcohols are prepared through their diastereomeric ester derivatives, subsequent acid hydrolysis of the latter to regenerate the alcohol may be accompanied by appreciable racemization.
With the advent of chromatography diverse variations on the basic theme of separating diastereomers became possible. These approaches undeniably represent substantial advances in the art, yet fail to surmount the basic need, and associated problems, to prepare diastereomeric derivatives of the desired compound and to transform such derivatives after separation to the optically active compounds of interest.
Chromatographic methods of separating diastereomers offer advantages of general application, mild conditions which generally preclude chemical or physical transformation, efficiency of recovery and separation which are limited only by the number of theoretical plates employed and the capability of utilization from a milligram to kilogram scale. Translation from a laboratory to industrial scale has proved feasible, and commercial processes employing chromatographic separation occupy an important position in the arsenal of available industrial methods. For such reasons, methods based on chromatographic separation remain under intensive exploration.
To circumvent the disadvantage of separating diastereomeric derivatives of a compound while retaining the advantage of chromatographic separation, recent advances in the art have employed chiral, optically active compounds in association with the chromatographic support. The theory underlying this approach is that chiral material will have differential weak interactions with enantiomers, for example, hydrogen bonding, or acid-base interactions generally. Such weak interactions lead to reversible formation of entities which we refer to as complexes, and the equilibrium constant characterizing complex formation will be different for each member of the enantiomeric pair. The different equilibrium constants manifest themselves as a differing partition coefficient among the phases in a chromatographic process, leading ultimately to separation of enantiomers.
Thus, enantiomers of some chromium complexes were resolved by chromatography on powdered quartz, a naturally occurring chiral material. Karagounis and Coumolos, Nature, 142, 162 (1938). Lactose, another naturally occurring chiral material, was used to separate p-phenylene-bis-iminocamphor. Henderson and Rule, Nature, 141, 917 (1938). However, despite this knowledge substantiating theoretical considerations, advances in the art have been tortuous at best.
A major obstacle has been development of a chiral solid phase capable of resolving, at least in principle, a broad class of racemic organic compounds, with a stability which permits repeated usage, and with adequate capacity to make separation feasible on a preparative scale. Gil-Av has made a major contribution toward one kind of solution by gas-liquid phase chromatographic resolution of enantiomers using columns coated with N-trifluoroacetyl derivatives of amino acids, di-and tri-peptides. Gil-Av and Nurok, xe2x80x9cAdvances in Chromatographyxe2x80x9d, Volume 10, Marcel Dekker (New York), 1974. However, the advances suffer practical limitations originating from the need to have volatile substrates and the inability to scale up the methods employed.
Another advance is represented by the work of Baczuk and coworkers, J. Chromatogr., 60, 351 (1971), who covalently bonded an optically active amino acid through a cyanuric acid linkage to a modified dextran support and utilized the resulting material in column chromatography to resolve 3,4-dihydroxyphenylalanine. A different approach is exemplified by polymerization of optically active amides with the resulting polymer used as a solid phase in liquid-solid chromatography. Blaschke and Schwanghart, Chemische Berichte, 109, 1967 (1976).
More recently it has become an accepted reality that enantiomeric medicinals may have radically different pharmacological activity. For example, the (R)-isomer of propranolol is a contraceptive whereas the (S)-isomer is a beta-blocker. An even more dramatic and tragic difference is furnished by thalidomide where the (R)-enantiomer is a safe and effective sedative when prescribed for the control of morning sickness during pregnancy whereas the (S)-enantiomer was discovered to be a potent teratogen leaving in its wake a multitude of infants deformed at birth. This has, in part, provided the motivation for developing additional tools for chiral separations. Chromatographic processes, especially liquid chromatography, appear to offer the best prospects for chiral separations. One variant of the latter utilizes achiral eluents in combination with chiral stationary phases (CSPs), which has the critical aspect that a variety of chiral stationary phases be available to the practitioner. In recent years substantial progress has been made by developing a class of chiral stationary phases based upon derivatized polysaccharides, especially cellulose, adsorbed on a carrier such as silica gel or a modified silica gel. This recently has been summarized by Y. Okamoto, J. Chromatog., 666 (1994), 403-19.
However effective may be the aforedescribed supports based on polysaccharides, there remains a need for chiral stationary phases where chirality is imparted by a monomer rather than by oligomers or polymers as represented by the polysaccharides. To be optimally useful the chiral monomer should have a plurality of chiral sites, so as to offer several chiral recognition sites and afford the potential of being broadly used in chiral separations. An appropriate monomer should afford a CSP based on covalent linkage of the monomer to the underlying carrier; covalently attaching the chiral monomer to a carrier virtually eliminates leaching, regardless of the mobile phase, and permits one to use many more types of mobile phases and to switch from forward to reverse phase eluents using the same column without fear of destroying the CSP due to leaching or plugging of the column. This benefit makes such CSPs much more effective for traditional single pass chromatography, for recycle-type chromatography, for simulated moving bed-based chromatography, and simple preferential adsorption of one enantiomer over the other.
The use of a monomeric chiral host containing several chiral centers providing a plurality of potential chiral interactions offers the possibility of a chiral stationary phase manifesting broad chiral discrimination. Yohimbinic acid is a chiral material with several easily derivatizable sites making this chiral host readily modifiable to xe2x80x9ctunexe2x80x9d its selectivity according to the racemate to be resolved. Covalent attachment of yohimbinic acid to the underlying carrier via its carboxylic acid function affords a useful series of chiral stationary phases, but use of the carboxylic acid functionality as the site of attachment does have some unwanted features. Modeling indicates that the chiral sites are more hindered by the surface of the carrier when yohimbinic acid is attached via the acid moiety as opposed to its attachment via the hydroxyl moiety. While some steric hindrance is desirable as a means to promote chiral selectivity, too much hindrance will actually limit access of both enantiomers to the active chiral sites, leading to decreased chiral recognition and poorer separations. Such hindrance will also decrease the number of different types of racemates which the chiral support can separate.
Attaching the yohimbinic structure to the carrier via the hydroxyl group instead of the acid moiety offers a slightly different chiral surface to the racemates. This variation increases the versatility of the yohimbinic acid structure, and it may also increase the number of possible racemates that may be separable. However, there are possible drawbacks to simply attaching yohimbinic acid to the carrier via the hydroxyl group. One is that the free acid moiety is likely to interfere with any reaction designed to couple the hydroxyl group to the carrier. Even if such a reaction is successfully carried out, there is a free carboxylic acid moiety available to interact with any racemate approaching the chiral discriminator since the carboxylic acid moiety is the most polar group in yohimbinic acid. In other chiral stationary phases where chiral recognition occurs using polar interaction, free carboxylic acid sites may significantly hinder, if not completely negate, chiral selectivity. Therefore, if the yohimbinic structure is to be attached to a carrier, it is desirable and perhaps imperative that the carboxylic acid moiety be blocked, as by forming an alkyl ester. Yohimbine is the methyl ester of yohimbinic acid.
In this application we take advantage of covalent attachment of yohimbinic acid esters, whose primary example is yohimbine, to the underlying carrier via the free hydroxyl group. The use of this monomer should lead to chiral stationary phases with good mass transfer properties more similar to brush-type stationary phases, whereas CSPs based on high carbon-loaded derivitized cellulosics show impaired mass transfer properties. Yohimbine-based CSPs according to our invention described within may be expected to be effective in both analytical and preparative chromatography, especially simulated moving-bed chromatography.
The purpose of our invention is to provide chromatographic processes for separating a mixture of racemates using a variety of covalently bonded chiral stationary phases based on yohimbine and analogous esters manifesting broad chiral discrimination. An embodiment uses yohimbine or an analogous ester of yohimbinic acid covalently bonded to an underlying silica carrier via an alkylsilyl spacer as the chiral stationary phase. A specific embodiment of this variant is one where a urethane group formed from the hydroxyl group of yohimbine and an isocyanato group is the covalent link bonding yohimbine to the spacer molecule. In a more specific embodiment the CSP is the yohimbine urethane of propylsilanized silica. Other embodiments will be apparent from our ensuing description.
The need for broadly-effective, xe2x80x9cgeneral-purposexe2x80x9d chiral stationary phases reflects the need for chiral stationary phases having 1) an organic monomer as the chiral recognition agent and 2) the potential to have broad chiral discrimination associated with a plurality of chiral sites. Because a CSP with covalently bound organic material can be expected to be more stable toward leaching and to afford somewhat greater flexibility in operating conditions, this type of CSP often is preferred over one where the organic material is merely coated on a carrier. Our invention fills these needs by using yohimbine and its analogs (i.e., the esters of yohimbinic acid) as the chiral organic material with a multiplicity of chiral recognition centers. Yohimbine and its analogs are covalently bound to the underlying carrier via an alkylsilyl spacer. Because yohimbine has multiple functionality, several sites may be derivatized independently to alter and customize chiral recognition for optimum resolution of specific enantiomeric pairs.
The chiral stationary phases of our invention consist of a carrier, which is a refractory inorganic oxide, and yohimbine or an analog thereof, where the yohimbine or analog thereof is covalently bound to the carrier via a spacer.
The carriers of our invention are refractory inorganic oxides which generally have a surface area of at least about 35 m2/g, preferably greater than about 50 m2/g and more desirably greater than 100 m2/g. There appears to be some advantage to working with materials having as high a surface area as possible, although many exceptions are known which preclude making this a general statement. Suitable refractory inorganic oxides include alumina, titania, zirconia, chromia, silica, boria, silica-alumina and combinations thereof. Of these, silica is particularly preferred as a carrier in chromatographic separations. Since the chiral stationary phase is yohimbine or an analog thereof covalently bonded to the underlying carrier, it is required that the carrier have bound surface hydroxyl groups, so that the latter may form one end of a tether which results from reaction of the bound surface hydroxyl groups with a silane functionality on a compound to form a covalent OSi bond as part of the structure, carrier-OSi-spacer. The progenitor of the spacer portion of our invention has the formula (RO)xSiHaly(CH2)nxe2x80x94NCO. The silane part of our spacer progenitor contains either halogen, Hal, or alkoxy groups, RO, either alone or in combination. Chlorine is by far the most common halogen which may be used in the practice of our invention, although bromine also may be used equally well. As for the alkyl group of RO, R may be any alkyl group, but preferably is a lower alkyl having from 1 through about 6 carbon atoms, with 1 and 2 carbon alkyl groups particularly desirable. The silicon atom is separated from the nitrogen atom by a chain of methylene groups, CH2. The length of this chain is given by n which is an integer between 1 and about 12, with n=2 to 4 especially desirable. The subscripts x and y also are integers where their sum is equal to 3. A suitable progenitor of the spacer portion of our invention merely has a nonreactive group between the silicon atom and the nitrogen of the isocyanato group. Thus, another equally viable progenitor of the spacer portion of our invention is one where the methylene chain is replaced by an aromatic group, as in
Similarly, substituted aromatic groups such as substituted phenyl groups are also suitable. Thus, the progenitor of the spacer portion of our invention may be expressed as (RO)xSiHaly(Q)nxe2x80x94NCO where Q is alkyl group, phenyl group, or substituted phenyl group. Other suitable progenitors will be apparent to the skilled worker. For ease of explanation, the discussion below depicts the progenitor of the spacer portion as a chain of methylene groups.
Yohimbine and its analogs in all cases constitute the chiral organic material in the chiral stationary phase of our invention. For convenience, yohimbine itself is given by the formula, (R1xe2x95x90CH3, R2xe2x95x90H).
One notes that yohimbine contains two centers other than the hydroxyl group which are easily substituted or derivatized, giving rise to the variables R1 and R2. R1 is selected from the group consisting of alkyl moieties containing from 1 up to about 20 carbon atoms, and aryl and aralkyl moieties containing from 7 up to about 20 carbon atoms, although the variant where R1 is a lower alkyl group containing 1 through about 6 carbon atoms is favored. R2 is selected from the group consisting of hydrogen, alkyl moieties containing from 1 up to about 20 carbon atoms, alkylaminocarbonyl moieties having 2 to 10 carbon atoms, arylaminocarbonyl moieties having 6 to about 10 carbon atoms, and acyl moieties containing from 2 up to about 20 carbon atoms.
Covalent bonding to the underlying carrier occurs via the hydroxyl portion of the yohimbine. A generalized representation of the resulting covalently bonded chiral stationary phase is given below:
The groups R1 and R2 have been defined above. The yohimbine or analog thereof may be present in an amount from about 0.2 up to about 8 wt. % based on the finished chiral stationary phase. Formation of the CSP results from the reaction of the isocyanate group in an isocyanotoalkylsilyl material with the hydroxyl functionality in yohimbine or an analog thereof to form a urethane linkage. Whether the urethane is first formed with later reaction of the silyl functionality with the bound surface hydroxyl groups of the carrier, or whether the urethane is formed after reaction of the silyl functionality with the bound surface hydroxyl groups of the carrier, is a matter of choice and is not fundamental to the outcome of our inventions. These two variants can be represented by the following equations (where ZOH represents yohimbine and its analogs).
As discussed earlier, the yohimbine-based CSPs are expected to be effective in both analytical, preparative, or industrial chromatography, and especially in simulated moving bed chromatography. The racemate to be separated is introduced to the yohimbine-based CSPs with the separated enantiomers being collected as product. Examples of specific racemates expected to be successfully separated by chromatographic processes using the yohimbine-based CSPs include racemic mixtures of: benzyl and substituted benzyl alcohols having a chiral center at the benzylic carbon; benzyl and substituted benzyl amines having a chiral center at the benzylic nitrogen; aromatic alkylamides and alkylamines where the amines or amides are part of or adjacent to a chiral center; N-acylated, esterified amino acids, benzoin, flavanone, indanol, tetralol, xcex1-methyl-2-naphthalenemethanol; 1-phenethyl alcohol, 2,2,2-trifluoro-1-phenylethanol; warfarin; 2,2,2-trifluoro-1-(9-anthryl)-ethanol; ester derivatives of aminoacids, NSAIDs (such as naproxen, ibuprofen, and ketoprofen); xcex2-blockers (such as propanolol, pindolol, and atenolol); verapamil, steroids, aryl-substituted hydantoins; sulfoxides; bi-2-napthols; bi-2-napthylamines, and benzodiazapines.
The example which follows merely illustrates some specific embodiments of our invention, which is not limited thereto. Other variants and embodiments will be clear to the skilled artisan.

Chromatographic process using a chiral stationary phase based on yohimbine


Process for the detection of a product in the discharge of a catalytic material of a plurality of catalytic materials which are exposed to a reaction gas, whereby an adsorbent selective for the product to be determined is disposed in the discharge of each catalytic material, which changes at least one of its properties through the contact with the product to be determined and the change in the property of the adsorbent is then ascertained.

The invention relates to a process for the detection of a product in the discharge of a catalytic material of a plurality of catalytic materials which are exposed to a reaction gas.
The development of new, especially more effective catalysts is required to improve the yield of many standard processes. In order to produce and characterise catalysts, the potentially active carrier and catalyst components are combined in a supposedly suitable manner and the multi-component mixtures thus created are tested with a suitable test reaction under defined conditions usually determined by technical limitations. Whilst the synthesis of such materials can often still be managed with reasonable time consumption, the testing of the catalysts on the contrary represents a very time- and labour-consuming step. The material to be tested is generally poured into a laboratory test reactor specially designed for the purpose and tested under prescribed parameters for its suitability for the given conversion of an educt mixture.
Gas chromatographic or spectroscopic methods are chiefly used to characterise catalysts. These methods, however, have only a limited suitability for the simultaneous testing of many catalysts. Whereas gas chromatography has the drawback that it requires a certain period of time, the spectroscopic methods have the drawback that, in the case of complicated reactions, they give insufficient information about the selectivities of the catalysts. Both methods also have the drawback that they only function sequentially and involve an elaborate and costly analysis.
Nonetheless, progress has been made with the applicability of both these methods. Through the computer-controlled combination of several columns, for example, an improvement has been achieved in the analysis quality and the analysis speed in gas chromatography (Stockinger, J. H., Callen, R. B., Kaufman, W. E., J. Chromatogr. Sci. 16, 1978, 418).
The use of spectroscopic methods for characterising samples is described in connection with a process for investigating chemical reactions in reactors connected in parallel (Windhab, N., Miculka, C., Hoppe, H.-U., DE 196 32 779).
A method of testing catalyst pellets with the aid of infrared thermography has also been published (Moates, F. C., Somani, M., Annamalai, J., Richardson, J. T., Luss, D., Willson, R. C., Ind. Eng. Chem. Res. 35, 1996, 4801). This method, however, is limited to reactions with great heat of reaction. An additional drawback with this method lies in the fact that, with partial oxidations for example, the hottest catalyst is not the one with the greatest selectivity for the desired product.
WO 97/32208 describes a catalyst testing process, in which a plurality of differently composed catalysts in the form of pellets or suchlike are arranged in a multi-cell holder and brought into contact with an inflow of a mixture. The measurement takes place spectroscopically, thermographically or with the aid of other commonly used measuring methods, whereby the measurement is always carried out directly on the catalysts.
DE 196 33 779 A1 describes a process for investigating chemical reactions in miniature reactors connected in parallel. The supplied educt is led past a catalyst in each case, as a result of which a reaction mixture arises which in turn is passed in each case into a cell drill-hole and separated out via the latter. For the measurement, an infrared beam extends in each case through one of the cell drill-holes which are arranged in the manner of an nxn matrix.
In the light of the prior art, the problem of the present invention is to make available an economically practicable process for the detection of a product in the discharge of a catalytic material of a plurality of catalytic materials which are exposed to a reaction gas, in order to establish the selectivity and activity of the catalytic materials.
Furthermore, the problem of the invention is to provide a method for the testing of catalytic materials that is as cost-effective, simple and efficient as possible.
The process should further be able to be carried out without taking a great deal of time and effort.
These problems, as well as other problems not explicitly stated but which can readily be derived or inferred from the context discussed herein, are solved by the measures described in claim 1. Expedient modifications of the process according to the invention are protected in the sub-claims related back to claim 1.
By disposing an adsorbent selective for the product to be determined in the discharge of each catalytic material, which changes at least one of its properties through the contact with the product to be determined, and then by ascertaining the change in the property of the adsorbent, it is possible to ascertain the selectivity and activity of the catalytic materials.
On the one hand, the process is cost-effective and efficient, and on the other hand the process can be carried out without taking a great deal of time and effort.
The arrangement for the analysis can be spatially separate from the catalytic material. The analysis of the products can thus be carried out by means of methods that cannot be used under the reaction conditions of the catalytic conversion, because for example the adsorbent is not stable at the temperatures at which the catalysed reaction must take place. If the adsorbent is not destroyed by the selected reaction conditions, it can however also be spatially very close to the catalytic material.
By means of a suitable arrangement of various adsorbents, different products of the catalytic reaction can be determined simultaneously. It is thus possible in a very elegant manner to determine, apart from the activity of a catalytic material in respect of a desired product, also the concentration of undesired by-products, so that the selectivity of the catalytic material can also be determined.
Preferred forms of embodiment of the process according to the invention are characterised by the fact that the adsorbent is a solid or a liquid applied to a solid carrier.
Preferably, an optical property, especially in the infrared, visible or ultraviolet region, is changed by the contact with the product to be determined.
It is particularly preferable for a colour change to occur through the contact of the adsorbent with the product of the catalytic conversion to be determined, so that for example a colour formation or a decolourisation can be ascertained.
It is further preferred that the property of the adsorbent changing through the contact with the product to be determined is a fluorescence.
A further property that can be changed by the contact with the product to be determined is the weight of the adsorbent.
A further preferred modification of the process according to the invention employs the temperature of the adsorbent to determine a product of the catalytic reaction.
A further property of the adsorbent that can be changed by the contact with the product to be determined is the refractive index of a liquid applied to a solid carrier.
Furthermore, the pH of the adsorbent is a property that can be changed by the contact with the product to be determined, especially when the adsorbent is a liquid applied to a solid carrier.
It is particularly preferable for a change in the conductivity of the adsorbent to occur through the contact with the product to be determined.
The product to be determined can also be dissolved out of the adsorbent with the aid of a solvent, after which a property, such as for example the refractive index, the pH value and the conductivity, of the solution thus obtained is determined.
Preferred forms of embodiment of the process according to the invention are characterised in that the product to be determined is maleic anhydride and the adsorbent is an N,N-dimethylindoanyline applied in ethanol solution onto a filter paper, whereby the colour of the adsorbent changes from blue to colourless upon contact with the maleic anhydride.
In a preferred form of embodiment of an adsorbent described above, reactive groups capable of reacting selectively with a desired product in the discharge of a parallel reactor are applied to a solid carrier.
In a further preferred form of embodiment, reactive molecules capable of reacting selectively with a desired product are dissolved in a solvent, after which the latter is applied to a solid carrier.
Detection of a product should be understood within the scope of the present invention to mean any identification of a chemical element, a chemical compound or a functional group which are formed in a catalytic reaction.
It can relate here, for example, to a compound whose formation is intended to be optimised by the catalytic conversion.
It is however also conceivable for a compound to be determined that necessarily arises with the formation of the desired product. Amongst others, this includes for example hydrogen which is liberated in a dehydrogenation.
By means of the process according to the invention, however, substances can also be detected whose formation is to be avoided, i.e. by-products of a catalytic conversion.
A catalytic material is a substance which lowers the activation energy for the course of a certain reaction and thus increases the reaction rate, without appearing in the end product of the reaction. Substance is understood here to mean for example elements and compounds as well as homogeneous and heterogeneous mixtures thereof. Binary or ternary mixtures of elements and/or compounds in particular often display an unexpectedly high catalytic effect which can only be ascertained empirically.
The process according to the invention makes it possible to investigate simultaneously under identical reaction conditions many catalytic materials which differ in their composition. The essential feature of the invention here is that the discharge of a catalytic material can be assigned to a change in the property of the adsorbent. It may be necessary here for the discharges of the respective catalytic materials to be kept separate from one another. The plurality of catalytic materials, i.e. at least two, can for example be introduced into parallel reactors.
Discharge is understood to mean the gas mixture after the contact with a catalytic material, which can contain at least one reaction product. The reaction gas is a gas that contains the reactant or reactants. It can in addition contain inert gases, such as for example nitrogen or noble gases (in particular helium, neon, argon or mixtures of these gases), in order for example to improve the conducting of the reaction.
Reactant is understood here to mean the starting substance or starting substances of a catalytic conversion. In a dehydrogenation, it can for example be an alkane, such as ethane. In other reactions, such as for example a hydrogenation or a partial oxidation, at least two reactants are required, such as for example hydrogen and an alkine in a hydrogenation, or oxygen and an alkane, such as n-butane in a partial oxidation.
Selectivity is the ability of the adsorbent to select preferentially one of a number of presented compounds in the discharge of the reaction gas.
Adsorbent designates a substance which is capable of concentrating at its boundary surface or absorbing into itself certain substances from gaseous mixtures, which can be linked to an increase in volume. The adsorbent can be a solid or a mixture of solids, such as for example activated carbon, aluminium oxide, silica gel, soot, zeolite, or liquid that is applied onto a solid carrier, such as for example an ethanol solution of N,N-dimethylindoanyline, which is applied to filter paper. These substances can also be used as a mixture. It is possible to provide the adsorbent with reactive groups or to load it with substances, in order thereby to bring about a selective change in property through the contact with the product to be determined.
Properties denote features of the adsorbent which are changed by the contact with the product to be determined. Amongst others, these included optical properties, especially in the infrared, visible or ultraviolet region of the spectrum, i.e. colour changes which can be traced back to the contact of the product with the adsorbent, such as an emergence of colour or a decolourisation, the weight of the adsorbent, the temperature, the fluorescence, the refractive index, the pH value or the conductivity.
The change in property occurring through the contact with the product to be determined must be ascertained according to the invention. Depending on the property, this can take place for example visually or by measurement. It is necessary here to adapt the measurement method to the change in property. A temperature change of the adsorbent that is based on a specific exothermal reaction can for example be determined by means of an infrared camera. The determination can also be automated in the majority of cases.

Abstract: The process serves in particular to determine the selectivity and activity of catalytic materials.


A rectangular insulated wire includes a rectangular conductor having a generally rectangular cross section, a thermosetting resin layer provided to cover the rectangular conductor, and a plurality of thermoplastic resin layers provided on the thermosetting resin layer. An adhesion strength between the thermosetting resin layer and the thermoplastic resin layer is 50 gf/mm to 100 gf/mm.

Technical Field
The present disclosure relates to an insulated wire obtained by coating a metal conductor with a resin, and particularly relates to an insulated wire used as a coil of an electric generator installed in, for example, electric power-driven vehicles.
Background Art
Conventionally, a round wire or a rectangular wire is employed as an insulated wire (magnet wire) used for a stator of an electric generator (motor generator) installed in automobiles. By employing a rectangular wire, a fill factor of the stator can be increased as compared to a case where a conductor having a generally round cross section is employed, and thus an electric generator having a reduced size and a higher power can be obtained. Recently, along with electric generators having a reduced size and higher power as described above, an insulated wire of the generator for vehicles is required to have properties, such as an insulating property, resistance to thermal softening, flexibility, and a long-term heat resistance, which are improved as compared to those of a conventional configuration.
In view of improving an insulating property, a so-called enameled wire having a rectangular conductor and an insulating layer of a thermosetting resin such as polyamide-imide (PAI) formed thereon is often used as a stator coil. However, an enamel coating alone does not provide sufficient reliability to high voltage. Accordingly, in order to improve the reliability to high voltage, attempts have been made to form another insulating layer on an outside of the enameled wire.
For example, some insulated wires have, on an outside of the enameled wire, another insulating layer formed of an amorphous resin such as polyethersulfone (PES). With this configuration, an insulating layer having excellent long-term heat resistance and insulating properties at a high voltage can be obtained. However, an amorphous resin such as PES is poor in chemical resistance. Therefore, when a coil is formed by winding an insulated wire and immersed into an impregnating varnish such as an epoxy resin, and thereafter, upon curing the impregnating varnish, the insulating layer formed of an amorphous resin is affected by the impregnating varnish and a crack tend to occur in the insulating layer.
In order to alleviate this, an insulated wire is proposed which is further provided with an insulating layer formed of a crystalline resin such as polyphenylene sulfide (PPS) or polyetheretherketone (PEEK) on an outside of the aforementioned insulating layer formed of an amorphous resin. With such a configuration, chemical resistance can be improved while maintaining the long-term heat resistance and the insulating property at a high voltage. However, the aforementioned configuration is poor in flexibility and resistance to thermal softening, since the crystalline resin such as PPS and PEEK has a small elongation and a low glass transition temperature. Furthermore, since a crystalline resin such as PPS and PEEK does not easily adhere to an amorphous resin such as PES, adhesion between these insulating layers is poor. Accordingly, a peeling occurs between the insulating layers in a bending process, which may result in a decrease in electrical characteristics.
Accordingly, an insulated wire has been proposed that has, on an outside of the enameled wire, a lower layer formed of PES and an upper layer formed on an outer surface of the lower layer, with the upper layer being formed of a polymer alloy of PES and PPS or of PES and PEEK (Japanese Laid-Open Patent Publication No. 2010-123390). By this configuration, since the upper layer is formed of a polymer alloy containing PES, adhesion with the lower layer formed of PES improves. Thus, occurrence of peeling between the upper layer and the lower layer which may occur in a bending process can be suppressed.
With the configuration in which the upper layer is formed of a polymer alloy, however, adhesion between the upper layer and the lower layer is greater than required. Accordingly, when the insulated wire is bent, a crack which extending from the insulating layer and reaching an outer surface of the conductor occurs, and thus it cannot be said that flex resistance reliability is sufficient. Further, recently, an electric generator disposed integrally with a transmission and configured to directly cool a heat generation portion using ATF (Automatic Transmission Fluid) retained in a motor case is being proposed as a vehicle electric generator. For insulated wires used for a coil of such electric generator, resistance to ATF is often required.
The present disclosure is related to providing a rectangular insulated wire having an improved flex resistance reliability by achieving both an improvement in adhesion between insulating layers and prevention of occurrence of a crack reaching a conductor, while maintaining flexibility and resistance to thermal softening, and further having an excellent ATF-resistant property, as well as an electric generator coil.

Rectangular insulated wire and electric generator coil


A personal harness can carry at least one article. The harness has a shoulder strap having a pair of carrying ends. The harness also has a pair of hitching devices for holding at least that one article. This pair of hitching devices is separately attached to the shoulder strap near the pair of carrying ends. Each of the hitching devices has a cinch strap, a clasp, and a primary slide. The primary slide is slidably mounted on the shoulder strap. The cinch strap is attached to the primary slide. The clasp can detachably join the cinch strap and the corresponding one of the carrying ends of the shoulder strap. The harness is used by encircling at least the one article with the shoulder strap and the respective cinch strap, with the clasp opened. After closing the respective clasp, one can carry at least that one article by shouldering the shoulder strap and walking.

1. Field of the Invention
The present invention relates to harnesses for carrying articles and in particular to a device having a shoulder strap and a clasp.
2. Description of Related Art
People often need to carry a large number of items when visiting the beach, shopping, skiing or engaging in any number of activities. Often the objects to be carried are cumbersome and a lightweight product is needed to facilitate such transportation.
For example in U.S. Pat. No. 5,165,584 a strap has on one end a loop for encircling the shoulder of an archer. The opposite end of the strap has an adjustable buckle and a quick release buckle leading to a Velcro band for encircling and holding a bow. This carrying device is dedicated to carrying a bow and is not easily adapted to carrying a variety of objects on either end of the strap.
U.S. Pat. No. 5,160,074 shows a strap with two forked ends employing Velcro fasteners to wrap around a pair of skis so they can be carried on a skier's shoulder. This device is dedicated to carrying skis and cannot be readily adapted for carrying a variety of articles such as large, bulky articles.
U.S. Pat. No. 4,676,417 shows another ski carrier that can be reconfigured after the skis are delivered and worn around the skier's waist. See also the ski carrying device of U.S. Pat. No. 4,903,875.
U.S. Pat. Nos. 4,867,359 and 4,953,768 show a network of shoulder straps and adjustable loops for carrying such articles as a golf bag or ski boots. See also U.S. Pat. Nos. 435,101; 4,911,347; 4,978,044; 5,119,910; and 5,143,266.
Accordingly, there is a need for a simple and lightweight device for carrying articles with a shoulder strap and employing loops that are easily adjusted and readily undone.