The present invention relates to a method for treating an inflammatory pathological condition in a patient in need thereof, comprising administering on empty stomach an anti-inflammatory effective amount of 2-methoxyphenyl-1-methyl-5p-methylbenzoyl-pyrrol-2-acetamido acetate (known also as amtolmetin guacyl and indicated in the present description also as MED 15).

Non-steroidal anti-inflammatory drugs (NSAIDs) have been used for many years in therapy. It is also well known that NSAIDs produce lesions to gastrointestinal apparatus depending on the length of the treatment and on the type of drug. This problem has a dramatic importance in cases where the therapy must be protracted for a long time. An example is rheumatoid arthritis in old people, where a chronic treatment is needed to keep under control the inflammatory state and the pain and make acceptable the quality of life.
At present there is a pharmacological dogma establishing a mandatory connection between anti-inflammatory effect and gastric lesions. This dogma has been recently shaken by the availability of newly synthesised anti-inflammatory drugs showing gastrolesive effects lower than those of old ones. Notwithstanding that equiactive doses of drug could produce lesions of different seriousness, it was settled that an anti-inflammatory drug showed, in any case, a gastrolesive effect. From this fact it followed that it could not be expected that these drugs known in the art could show a gastroprotective effect.
It is also well known, and this has a pharmacological relevance too, that the administration of NSAIDs reflects negatively on renal function, in particular by provoking a remarkable decrease in diuresis. This effect is due to prostaglandin blockade; in fact, prostaglandin physiologically dilate the renal vascular system. The blocking effects of traditional NSAIDs lead to vasoconstriction and to the consequent inhibition of diuresis. From this fact it followed that it could not be expected that these drugs known in the art could be administered without negatively affecting the renal function.
Even more so in view of the above, it could not be expected that a NSAID could simultaneously show a gastroprotective effect without negatively affecting the renal function while at the same time maintaining a high anti-inflammatory activity.
It is also well known that in view of their side-effects on gastric mucosa, NSAIDs are invariably administered after meals or, in general, when the stomach is not empty. The generality of this pharmacological principle finds a practical confirmation in the recommendations found in the packagings of the drugs in commerce. Basically the idea is that the effects of the hypersecretion of hydrochloric acid provoked by the administration of NSAIDs may be, at least partially, counteracted by the presence of food.
It has been now surprisingly found that the compound 2-methoxyphenyl-1-methyl-5p-methylbenzoyl-pyrrol-2-acetamido acetate, which is an effective anti-inflammatory non-steroidal drug as already known in the art, shows a remarkable antisecretory activity on gastric secretion in mammals without affecting the renal function, but, on the contrary, increasing the diuresis. This increase in diuresis is linked to its mechanism of action; in fact, the overflow of neuropeptides (in particular CGRP) produced in the stomach by MED 15 and flowing from the stomach into the bloodstream, produces renal capillary vasodilatation, with reversal of its effect on prostaglandin.
Additionally, and more than unexpectedly for a NSAID, it has been found that amtolmetin guacyl, in order to show its efficacy (gastroprotection and renal tolerability together with an anti-inflammatory effect unchanged), has to be administered on empty stomach in view of the peculiarity of its action mechanism.
The compound 2-methoxyphenyl-1-methyl-5p-methylbenzoyl-pyrrol-2-acetamido acetate is already known in the art and is for instance disclosed in Italian patent application no. 47881A/82 and in U.S. Pat. No. 4,578,481 issued on Mar. 25, 1986.
Both the documents of the state of the art disclose that the above compound shows anti-inflammatory, analgesic, antipyretic, antitussive and antisecretive (on the mucus of the respiratory airway) properties. No mention, either direct or indirect, is made about a possible antisecretive effect on the gastric secretion in mammals.
It is therefore the subject matter of the present invention a method for treating an inflammatory pathological condition in a patient in need thereof, comprising administering on empty stomach an anti-inflammatory effective amount of 2-methoxyphenyl-1-methyl-5p-methylbenzoyl-pyrrol-2-acetamido acetate.

Method for treating an inflammatory pathological condition


A rotary engine includes a housing body having a first rotation chamber and a second rotation chamber. A first rotary body is arranged within the first rotation chamber, and a second rotary body is arranged within the second rotation chamber. A boundary surface of the first rotation chamber has a variable distance from an opposite surface of the first rotary body. A pair of valve flaps having a first valve flap and a second valve flap is arranged on the first rotary body. Upon rotation of the first rotary body, the valve flaps are in engagement with the boundary surface of the first rotation chamber and are rotated in mutually opposite directions with regard to the first rotary body so as to form two mutually demarcated working chambers within the first rotation chamber.

EP 1 405 996 A1 describes a rotary engine on the basis of a thermodynamic process. The rotary engine is shown in FIG. 9, the advantages are referred to by the inventors as increased fuel efficiency and simple manufacture of the rotary engine as compared to thermodynamic machines known to date. In the rotary engine shown, two rotary bodies counter rotate, a first rotary body being arranged within the working chamber, and a secondary rotary body being arranged within the compression chamber. A working medium is fed into the compression chamber by the rotary body located within the working chamber, where it is ignited separately from the working chamber and is fed back to the working chamber, where it carries out work by expanding and thus driving the rotary body located within the working chamber. A disadvantage of the machine described in said document is that slides are inserted into both rotary bodies for seals of the working chamber and compression chamber, which slides are pressed outward upon rotation of the rotary bodies, due to the arising centrifugal forces, against an inner housing wall of the housing 1 of the rotary engine so as to thereby be able to compress the medium. However, said slides are subject to a large amount of wear and tear, and the contact pressure of the slides to the inner housing wall and, thus, the tightness are based only on the arising centrifugal force upon rotation of the rotary bodies, or on springs arranged between the slide elements and the rotary body. Over time, said springs may lose their tensional force, which may result in a leak in the working chamber and the compression chamber. What is also disadvantageous is that the two rotary bodies move in opposite directions while being in constant contact, which leads to increased friction of the rotary bodies: this results either in a large amount of wear and tear or in utilization of costly, low-wear materials on surfaces of the rotary bodies.


The power supply unit is provided with a power supply circuit adapted to generate an output voltage in accord with an instruction voltage, an output condenser Co connected to the output end of the power supply circuit, and an auxiliary output voltage setting circuit adapted to compare the instruction voltage and the output voltage and to cause the output condenser to discharge its electric charge when the instruction voltage becomes lower than the output voltage. Because of the auxiliary output voltage setting circuit, the power supply circuit quickly generates an output voltage in accord with the instruction voltage if the instruction voltage is lowered.

Switching power supply units have been widely used as power supply units for efficiently converting a given supply voltage to a lower voltage. In order to smooth the intermittent output voltage arising from switching, a switching power supply unit has at the output end thereof a smoothing coil and an output condenser.
The smoothing coil and the output condenser will delay the output voltage if a load is suddenly changed. Thus, there has been proposed an improved power supply unit adapted to alleviate the delay in the response to a change in load, as disclosed in, for example, Japanese Patent Early Publication H10-98874.
FIG. 1 shows a general circuit arrangement of a power supply unit having an improvement in response to a delay pertinent to conventional circuits. A switching power supply circuit 1 of FIG. 1 performs switching to convert a supply voltage Vin of a power source B such as a battery into a pulsed output having a fixed pulse width, based on the comparison of the output voltage Vo with an internal reference voltage (not shown). The pulsating output is smoothed by a smoothing coil Lo and an output condenser Co, and supply a resultant output voltage Vo to a load 3. Diode D is a flywheel diode.
If this load 3 suddenly increases, the output voltage Vo is lowered. In order to compensate for the delay in recovery of the output voltage Vo back to a predetermined level, a series power supply circuit 2 is connected in parallel with the switching power supply circuit 1. Thus, when the output voltage Vo is suddenly lowered by a sudden increase of the load, a current is promptly supplied to the output condenser Co via the series power supply circuit 2, thereby recovering the output voltage Vo within a short delay time.
In this conventional electric power supply unit, the output voltage can be recovered without an appreciable delay even if a rapid change takes place in the load, provided that the power supply unit has a fixed reference voltage. However, in cases where the reference voltage is lowered to change the output voltage, the conventional electric power supply unit cannot quickly lower the output voltage because the series power supply circuit 2 has only a current-feeding capability.
FIG. 2 shows the reference voltage Vref, output voltage Vo, and load current Io changing in time during a transitional discharge. Suppose now that the reference voltage Vref is dropped from an initial level Vref1 to a final lower voltage Vref2 at time t1, as shown in FIG. 2(a). Then the current Io flowing through the smoothing coil slowly decreases as shown in FIG. 2(c), because the discharge by the load 3 is slow and that a back electromotive force is generated by the smoothing coil Lo. Consequently, the output voltage Vo sluggishly changes from its initial level Vo1 to a final level Vo2 associated with the reference voltage Vref2 over a period T2, as shown in FIG. 2(b). It is noted that the waveform of current Io shown in FIG. 2(c) corresponds to substantial switching of the output transistor of the switching power supply unit.
It is, therefore, an object of the present invention to provide a power supply unit having an output condenser, the unit adapted to change its output voltage quickly to the target voltage defined by a variable output voltage setting.

This patent is subject to a terminal disclaimer.

Electric power supply unit having improved output voltage response


A preform for use in forming orthotic devices which have a memory in the original preform shape. The preform is preferably formed into a final body shape which retains a memory of the original preform shape.

A wide variety of orthotic devices are known for use in correcting body problems or supporting body structures such as broken or displaced bones, strained or stretched tendons and ligaments or post-surgical repair.
Most orthotic devices which are custom made of thermoplastic polymeric materials use flat sheets as starting materials. The flat sheets are heated and softened, draped over molds cooled and hardened, thus forming a finished part. The molds used are generally made from plaster and this requires the taking of plaster impressions from the body part such as an arm or foot region with later formation of a positive mold made from the plaster negative mold.
In some cases, the draping process can be assisted by vacuum forming, pressure forming or other common molding techniques. These products, whether or not formed directly around the body, have a disadvantage in that they produce oversized parts which must be cut to size and then finished, usually in hand operations. The cutting and finishing times can be lengthy and time-consuming.
Conventional plastics used where molds are draped, generally have too high a temperature when moldable to be applied directly to the body and formed.
More recently, in another method of making orthotic devices, low temperature polymeric materials or plastics are used. These plastic materials become malleable at a relatively low temperature as, for example, between 150.degree.-160.degree. F. and can be applied directly to the body so as to obtain the correct body shape while molding. In some cases, flat sheets of such low temperature plastic materials can be pre-cut to the amount of preliminary preparation and to reduce the amount of secondary finishing.
When complex shapes are made or the amount of forming is large, there is some difficulty. In some cases, the low temperature plastics tend to be thinned in critical areas and in an uncontrolled way. This can weaken and reduce the rigidity of the orthosis in an undesirable way.
Plastics formed by conventional techniques from sheet material also have the tendency to revert to their original shape as, for example, the flat sheet from which they are made. Sometimes a formed orthotic must be reheated and modified. Reversion to the original flat sheet often prohibits such a modification, especially if the original orthotic was trimmed. Such reversion is generally due to the processing characteristics of the plastic. For example, in sheet formation, some stretching and orientation may occur in manufacture and in some cases, if the sheet is anisotropic and subsequently cross-linked, there is a tendency to bring the material back to sheet form under certain conditions of use. Such conditions of use are usually those conditions that exceed normal general use but are present on extremely hot days. Also, should a complete, shaped orthotic be reheated for subsequent modification, it returns to its original flat shape.

Polymeric orthotic devices and method of formation


A television system having sync suppression scrambling and descrambling which includes in band and out of band signaling methods. The in band signaling method modulates the IF sound carrier of a premium video channel with timing and data pulses while the out of band signaling method modulates the previously modulated IF sound on a separate carrier onto a separate out of band data carrier. The in band signaling method uses a descrambler which tunes a channel before demodulating the timing and data pulses from the sound carrier while the out of band signaling method tunes a selected data carrier to demodulate the timing and data pulses. In both methods, the timing pulses are used to restore the levels of the synchronization pulses in the sync suppressed video signal, and thus descramble the signal, while the data pulses are used for addressable messaging to the descrambler including authorization. The out of band descrambler provides broadband sync restoration for a particular channel and thus does not need a broadband tuner for the video signal.

Although the invention is not necessarily limited thereto, it is particularly suitable for use and transmission of subscription TV programs by cable systems. The invention may also be applied wherever sync suppression scrambling and descrambling of television signals is used whether the transmission link is a cable, broadcast, or satellite link.
Sync suppression scrambling and descrambling of television signals is a well known and accepted technique for encoding and decoding subscription television signals where the amplitude of the vertical or horizontal synchronizing (sync) signals, or both, is attenuated so as to prevent a television receiver from locking onto the signal. The picture received by a subscriber receiver not equipped with a descrambler rolls and is so distorted so as to make viewing impossible or uncomfortable. Reference may be had to U.S. Pat. No. 4,466,017 issued to Robert Banker on Aug. 14, 1984 for further information as to sync suppression scrambling and descrambling of television signals. The disclosure of Banker is incorporated herein by reference.
Briefly described, sync suppression scrambling and descrambling of TV signals for subscription TV programs may be carried on by generating sync suppression pulses in overlapping time relationship with the horizontal and/or vertical sync pulses of the TV signal. Timing pulses are generated in selected time relationship with the sync suppression pulses such that each of the timing pulses and the sync suppression pulses have a selected time delay with respect to each other. This time delay may be selected, preferably digitally, from a plurality of different delays or dynamically varied. The horizontal and/or vertical sync pulses in the television signal are thereby suppressed below their normal amplitude. Sync detectors of conventional TV receivers at the subscriber are incapable of locking onto the attenuated sync pulses of the transmitted television signal. The timing pulses are transmitted with the TV signals, preferably by modulating the IF audio carrier thereof, during encoding of the TV signals. Scrambled and encoded TV signals are transmitted from a transmitting station which may be, for example, the headend of a cable TV system, to the receiving stations.
The timing pulses are derived at these receiving stations and the selected delay added to generate delayed timing pulses. Then restoring pulses are generated in proper overlapping time relationship with the received horizontal sync pulses upon the occurrence of the delayed timing pulses. The TV signals are restorable to normal amplitude through the use of the restoring pulses to descramble the TV signals. Therefore, the receiving station to restore the pulses in synchronism with the horizontal sync intervals of the TV signals must be not only authorized to receive the scrambled signals but also be tuned to the particular premium channel which is scrambled. Other premium channels which are scrambled are usually out of phase with a particular timing signal and cannot be descrambled without being tuned. In the past the duplication of the tuner in a converter/descrambler and a cable ready TV was considered inevitable.
After tuning in the particular TV premium channel which is to be descrambled and decoding the timing pulses, the descrambling process is one of restoring the horizontal sync pulses to their original level relative to the rest of the TV signal. This is generally accomplished by a controlled impedance device, either an attenuator or an amplifier, which is placed in series with the signal and at the correct times switched on and off to vary its impedance and thus the amplitude of the synchronization pulses relative to the rest of the signal.
Conventional descramblers used in subscription cable television to descramble the sync suppression signals from a headend usually contain a converter or tuner. In many, the output frequency of the CATV converter is fixed, such as channels 2, 3, or 4, requiring that all channel changing must be done through the CATV converter. In addition, this is a redundant function where the CATV converter has a tuner whose operation closely duplicates that of the tuner in a cable ready television receiver and adds a significant increase to the cost of the CATV converter along with some degradation of the TV signal.
An additional problem in developing descramblers which are compatible with the present CATV systems is the compatibility of signaling methods. Authorization information and data for other operations are transmitted in band and out of band for various systems. An in band signaling system frequently utilizes the sound carrier by modulating it with timing and data pulses. This does not affect the sound, which is frequency modulated on the carrier. For out of band systems, a single FM modulated signal is set aside for authorization messages with no timing data included thereon. It would be highly advantageous for a descrambling apparatus to be compatible with the CATV system in which it is placed without having to replace other converters because of incompatible message protocols.

System for broadband descrambling of sync suppressed television signals


The invention provides a green process for direct oxidation of a large number of substituted or unsubstituted cinnamaldehydes or cinnamyl alcohols into the corresponding alkyl or aryl cinnamates in one step. The process of the present invention is a convenient and efficient green process for the preparation of various aryl or alkyl cinnamates under conventional, microwave and ultrasound directly from cinnamaldehydes or cinnamyl alcohols in the presence of an oxidizing agent, catalyst and an alcohol, with or without an organic solvent. These esters are immensely important compounds in flavor, perfumery and pharmaceutical industries. There are several prior arts available for the preparation of cinnamic esters, but all of them suffer from deficiencies such as use of expensive reagents and catalysts, harsh reaction conditions, use of toxic chemicals and others. In contrast, the present methodology is extremely simple and involves reaction of the substrate with an oxidizing agent mixed with a homogeneous or heterogeneous catalyst and an alcohol with or without organic solvent by stirring at room temperature or refluxing or under microwave or ultrasound irradiation to get the requisite products.

1. Field of the Invention
The present invention relates to a single step Green Process for the Preparation of Substituted Cinnamic Esters with trans-Selectivity. The present invention particularly relates to a process of conversion of cinnamyl alcohol or cinnamaldehyde to corresponding esters directly. Cinnamic esters are commercially important products in cosmetics, lubricants, plasticizers and perfumes.
2. Background Information
Cinnamic esters are immensely important organic compounds due to their applications in a wide range of products such as cosmetics, lubricants, plasticizers and perfumes (A. Steffen, Perfume and Flavor Chemicals (Aroma Chemicals), Vol. I & II. Allured Publishing Corporation: IL, USA, 1994). These esters are useful as a material for perfumes, as cinnamic aldehydes, and for the synthesis of β-amyl cinnamic aldehydes and the like. These esters can themselves be used as precursors for the synthesis of polyhetroalkylene esters which can be useful as raw materials for the synthesis of perfumes, drugs and as organic synthetic intermediates and as polymerisable materials and so forth (K. Yurugi, T. Kubo, U.S. Pat. No. 6,541,656, 2003).
A number of prior arts are available for the synthesis of cinnamic esters (A. Galat, J. Am. Chem. Soc., 1946, 68, 376; V. T. Ramakrishnan, J. Kagan, J. Org. Chem., 1970, 35, 2901; H. Tanaka, S. Takamuku, H. Sakurai, Bull. Chem. Soc. Jpn., 1979, 52, 801; Y. Oikaw, T. Yoshioka, O. Yonemitsu, Tetrahedron Lett., 1982, 23, 889; U. Tataki, I. Suso, T. Matsuhisa, I. Hara, U.S. Pat. No. 4,661,620, 1987; B. Gerhard, K. Jochen, S. Werner, U.S. Pat. No. 5,124,478, 1992; Z. Wang, F. R. W. McCourt, D. A. Holden, Macromolecules, 1992, 25, 1576; T. Iliefski, S. Li, K. Lundquist, Tetrahedron Lett., 1998, 39, 2413; V. L. Pardini, S. K. Sakata, R. R. Vargas, H. Viertler, J. Braz. Chem. Soc., 2001, 12, 223; H. Weissman, X. Song, D. Milstein, J. Am. Chem. Soc., 2001, 123, 337; K. M. Bushan, G. V. Rao, T. Soujanya, V. J. Rao, S. Saha, A. Samanta, J. Org. Chem., 2001, 66, 681; A. Stadler, C. O. Kappe, Tetrahedron, 2001, 57, 3915; P. Kisnaga, B. Dsa, J. Verkade, Tetrahedron, 2001, 57, 8047; B. Deevi, J. R. Anumolu, Synth. Commun., 2002, 32, 195; C. S. Cho, D. T. Kim, H. J. Choi, T. J. Kim, S. C. Shim, Bull. Korean Chem. Soc., 2002, 23, 539; R. Borah, D. J. Kalita, J. C. Sarma, Ind. J. Chem., 2002, 41B, 1032; S. F. Jonathan, K. Hisashi, M. P. G. Gerard, J. K. T. Richard, Synlett, 2002, 8, 1293; S. Crosignani, P. D. White, B. Linclau, Org. Lett., 2002, 4, 2961; O. Uchikawa, K. Fukatsu, R. Tokunoh, M. Kawada, K. Matsumoto, Y. Imai, S. Hinuma, K. Kato, H. Nishikawa, K. Hirai, M. Miyamoto, S. Ohkawa, J. Med. Chem., 2002, 45, 4222; A. Costa, C. Nájera, J. M. Sansano, J. Org Chem., 2002, 67, 5216; W. C. Shieh, S. Dell, O. Repic, Tetrahedron Lett., 2002, 43, 5607; A. Palma, B. A. Frontana-Uribe, J. Cardenas, M. Saloma, Electrochem. Commun., 2003, 5, 455; S. Crosignani, P. D. White, R. Steinauer, B. Linclau, Org. Lett., 2003, 5, 853; H. M. S. Kumar, M. S. Kumar, S. Joyasawal, J. S. Yadav, Tetrahedron Lett., 2003, 44, 4287; N. N. Karade, S. G. Shirodkar, R. A. Potrekar, Synth. Commun., 2004, 34, 391; R. B. Andrew, C. G. IV Louis, Synlett, 2004, 738; T. J. Speed, J. P. McIntyre, D. M. Thamattoor, J. Chem. Edu. 2004, 81, 1355; D. Penningt, M. A. Russell, B. B. Chen, H. Y. Chen, B. N. Desai, S. H. Docter, D. J. Edwards, G. J. Gesicki, C. D. Liang, J. W. Malecha, S. S. Yu, V. W. Engleman, S. K. Freeman, M. L. Hanneke, K. E. Shannon, M. M. Westlin, G. A. Nickels, Bioorg. Med. Chem. Lett., 2004, 14, 1471; J. M. Concellon, H. R. Solla, C. Mejica, Tetrahedron Lett., 2004, 45, 2977; D. K. Barma, A. Kundu, A. Bandyopadhyay, A. Kundu, B. Sangras, A. Briot, C. Mioskowski, J. R. Falck, Tetrahedron Lett., 2004, 45, 5917; R. Ballini, D. Fiorini, A. Palmieri, Tetrahedron Lett., 2004, 45, 7027; G. Deng, B. Xu, C. Liu, Tetrahedron, 2005, 61, 5818). The most common being acid catalysed esterification of the cinnamic acids in the presence of appropriate alcohols ((a) I. A. Pearl, D. L. Beyer, J. Org. Chem., 1951, 16, 216; (b) L. H. Klemm, R. A. Klemm, P. S. Santhanam, D. V. White, J. Org. Chem., 1971, 36, 2169; (c) B. Botta, G. D. Monache, M. C. De Rosa, A. Carbonetti, E. Gacs-Baitz, M. Botta, F. Corelli, D. Misiti, J. Org. Chem., 1995, 60, 3657; (d) A. Ewenson, B. Croitoru, A. Shushan, U.S. Pat. No. 728,865, 1998; (e) A. M. S. Silva, I. Alkorta, J. Elguero, V. L. M. Silva, J. Mol. Struct., 2001, 595), however, the reaction is reversible and the acids employed may not be compatible with many sensitive functional groups attached at either the aromatic ring or the alkyl chains such as alkoxy, halogens and the like.
Similarly, Org. Synth. Coll. Vol. 1, 252, discloses a method for the preparation of ethyl cinnamate by reaction of benzaldehyde, ethylacetate and ethanol and sodium as dispersed pieces. However, the process suffers from the use of highly inflammable sodium. Another conventional approach for the synthesis of cinnamates is the Claisen condensation between benzaldehydes and acetic acid esters (A. I. Vogel, A Textbook of Practical Organic Chemistry, Richard Clay (The Chaucer Press), Ltd., Bungay, Suffolk, 1978) in the presence of a strong base such as sodium salts of acetic acids and again the method has limitation for a number of substituted benzaldehydes. Moreover, the reactions are reported to take invariably long time for completion which adds to the mundane of the chemists and unnecessarily utilize energy resources in industries.
Heck came up with a different route for the synthesis of α,β-unsaturated acids (Heck. et al., J. Amer. Chem. Soc., 1969, 6707) by reaction between aryl halides and aryl acrylate using palladium acetate and a base as catalyst. Although, the method provided good yield of the product, it still suffers from expensive reagents used in the reaction.
Another modification of Heck reaction came in the form of Stille reaction (Stille et al., J. Amer. Chem. Soc., 1976, 1806) wherein alkyl boronic acids are being taken as the substrates and are reacted with aryl halides. However, the reaction also requires presence of copper salts (II) in stoichiometric amounts as oxidants in these reactions.
The following prior art references are disclosed:
Commetti and Chiusoli (J. Organometal. Chem., 1979, 181, C14) discloses a method for synthesis of methyl cinnamate by reaction of styrene, carbon monoxide and methanol in the presence of palladium as catalyst, but again it has a shortfall in terms of use of excess Cu (II) salt as oxidant which renders the process industrially unviable.
Similarly, many patents disclose the method for the preparation of cinnamic esters as discussed below:
J.P. Pat. No. 21342 discloses a method for the production of methyl cinnamate through oxidative carbonylation of styrenes wherein it was further disclosed that use of an excess dehydrating agent may cause increase in the yield the product and good yields could be obtained. However, use of excess dehydrating agent was an impediment in this transformation.
J.P. Pat. No. 21343 discloses a method for the production of methyl cinnamates by reacting styrenes, aliphatic alcohols, carbon monoxide and palladium but again the method has its drawback in the form of using expensive dehydrating agent.
U.S. Pat. No. 4,737,591, 1988 discloses a method for the cinnamate derivatives by reacting styrenes, aliphatic alcohols, carbon monoxide, palladium chloride and copper salt without any dehydrating agent, but poor yield of the product was obtained.
D.E. Pat. No. 7,099,227 discloses a method for the preparation of ethyl cinnamate by condensing benzaldehyde and ethyl acetate in the presence of sodium hydride as a base. Sodium hydride, however, is not easy to handle and is expensive and so the process demands improvement.
U.S. Pat. No. 4,618,698, 1986 discloses a method for the preparation of optionally substituted cinnamic acid by treatment of optionally substituted benzaldehyde and acetic acid ester and alcohol to form an optionally substituted cinnamic acid ester as well as alkoxy phenyl propionic acid which then was hydrolyzed into optionally substituted cinnamic acid. This was finally esterified to provide the cinnamic ester. The reaction suffers from tedius of multi step synthesis and demands rectification.
U.S. Pat. No. 6,054,607, 2000 discloses a method for the preparation of cinnamic acid esters by condensing a benzaldehyde with an acetic acid ester in the presence of a base followed by treatment with an acid to form alkoxy phenylpropionic acid ester which is then treated with an acid to provide the cinnamic ester. In addition, many patents (U.S. Pat. Nos. 3,381,030, 3,397,225, 3,397,226, 3,530,168, 3,621,054) also discloses the method for the preparation of cinnamic esters. Though, the many above mentioned methods provide good yield of the product, the reaction conditions are not mild and resort to ultra low temperature there by making it difficult to control the reaction.
In 1968, Corey, Gilman and Ganem presented a unique approach of converting α,β-unsaturated aldehydes directly into their methyl esters using manganese dioxide, sodium cyanide and acetic acid in methanol (E. J. Corey, N. W. Gilman, B. E. Ganem, J. Am. Chem. Soc., 1968, 90, 5616). This revolutionary method made a remarkable impact in organic chemistry and has been instrumental in the synthesis of various complex natural products (E. J. Corey, J. A. Katzenenllenbogen, N. W. Gilmen, S. A. Romen, B. W. Erickson, J. Am. Chem. Soc., 1968, 90, 5618; A. D. Adams, R. H. Schlessinger, J. R. Tata, J. J. Venit, J. Org. Chem., 1986, 51, 3070).
The above method continued to attract the attention of researchers for direct conversion of aldehydes or alcohols into esters and various prior arts are available for this conversion using a range of reagents such as MnO2—NaCN (A. B. III Smith, G. A. Sulikowski, M. M. Sulikowski, K. Fujimoto, J. Amer. Chem. Soc., 1992, 114, 2567; J. S. Foot, H. Kanno, G. M. P. Giblin, R. J. K. Taylor, Synlett, 2002, 1393), chromium oxide-pyridine (E. J. Corey, B. Samuelsson, J. Org. Chem., 1984, 49, 4735), t-butyl hypochlorite (J. N. Milovanovic, M. Vasojevic, S. Gojkovic, J. Chem. Soc. Perkin Trans 2, 1991, 1231) and PhIO—KBr (H. Tohma, T. Maegawa, Y. Kita, Synlett, 2003, 723) etc. There are other prior arts such as Tetrahedron Lett., 1982, 23, 4647; Tetrahedron, 1982, 38, 337; J. Org. Chem., 1968, 33, 2525; J. Amer. Chem. Soc., 1976, 98, 1629 etc for the preparation of esters.
Although methods for direct conversion of cinnamaldehyde (C6-C3 unit) or cinnamyl alcohol (C6-C3 unit) into cinnamic esters (C6-C3 unit) are meritorious but have certain limitations. First, all these methods pass through an intermediate C6-C4 unit, formed by combination of substrate C6-C3 unit and an extra C1 unit in the form of sodium/potassium cyanide or TMSCN (B. S. Bal, W. E. Childers Jr., H. W. Pinnick, Tetrahedron, 1981, 37, 2091; A. D. Adams, R. H. Schlessinger, J. R. Tata, J. J. Venit, J. Org. Chem., 1986, 51, 3070) etc. and overall, the protocols confer lack of atom economy. Secondly, use of hazardous cyanide reagents make the process more and more unviable for industrial use. In the contemporary concerns for Green chemistry, there has been a tremendous upsurge of interest in various chemical transformations mediated by Green technologies (T. J. Mason, P. Cintas in Handbook Of Green Chemistry and Technology (Eds.: J. Clark, D. Macquarrie), Blackwell Publishing, 2002, pp. 372) such as atom economical processes, reactions in aqueous media, reusable heterogeneous catalysts, use of ultrasound and microwave (B. L. Hayes, Microwaves Synthesis: Chemistry at the Speed of Light, CEM Publishing: Matthews N.C., 2002; N. F. K. Kaiser, U. Bremberg, M. Larhed, C. Moberg, A. Hallberg, Angew. Chem. Int. Ed., 2000, 39, 3596; P. Lidstrom, J. Tierney, B. Wathey, J. Westman, Tetrahedron, 2001, 57, 9225; M. Larhed, A. Hallberg, Drug Discov. Today, 2001, 6, 406; A. K. Bose, M. S. Manhas, S. N. Ganguly, A. H. Sharma, B. K. Banik, Synthesis, 2002, 11, 1578; K. J. Watkins, Chem. Eng. News, 2002, 80, 17; N. E. Leadbeater, H. M. Torenius, J. Org. Chem., 2002, 67, 3145; L. Botella, C. Nájera, Tetrahedron Lett., 2004, 60, 5563; N. Kaval, W. Dehaen, P. Mátyus, E. V. Eycken, Green Chem., 2004, 6, 125; V. Pathania, A. Sharma, A. K. Sinha, Helv. Chim. Acta, 2005, 88, 811; B. P. Joshi, A. Sharma, A. K. Sinha, Tetrahedron, 2005, 61, 3075) for organic transformations.
Cinnamic esters are of immense importance in organic chemistry due to synthetic utility ((a) T. Ohno, Y. Ishino, Y. Sumagari, I. Nishiguchi, J. Org. Chem., 1995, 60, 458; (b) B. Botta, G. D. Monache, M. C. De Rosa, A. Carbonetti, E. Gacs-Baitz, M. Botta, F. Corelli, D. Misiti, J. Org. Chem., 1995, 60, 3657; (c) F. Xu, R. D. Tillyer, D. M. Tschaen, E. J. J. Grabowski, P. J. Reider, Tetrahedron Asymmetry, 1998, 9, 1651; (d) M. Carmignani, A. R. Volpe, F. D. Monache, B. Botta, R. Espinal, S. C. De Bonnevaux, C. De Luca, M. Botta, F. Corelli, A. Tafi, G. Ripanti, G. D. Monache, J. Med. Chem., 1999, 42, 3116; (e) G. Li, H. X. Wei, S. H. Kim, Org. Lett., 2000, 2, 2249; (f) H. X. Wei, S. H. Kimm, G. Li, Tetrahedron, 2001, 57, 3869; (g) G. Li, H. X. Wei, S. H. Kim, Tetrahedron, 2001, 57, 8407; (h) R. K. Lamni, A. Ambroise, T. Balasubramanian, R. W. Wagner, D. F. Bocian, D. Holten, J. Lindsey, J. Amer. Chem. Soc., 2002, 122, 7579) of the ensuing cinnamic esters beside their applications in a wide range of products such as cosmetics, lubricants, plasticizers and perfumes (A. Steffen, Perfume and Flavor Chemicals (Aroma Chemicals), Vol. I & II. Allured Publishing Corporation: IL, USA, 1994). More importantly, these esters possess a variety of pharmacological activities including antioxidant (J. Chalas, C. Claise, M. Edeas, C. Messaoudi, L. Vergnes, A. Abella, Biomed. Pharmacother., 2001, 55, 54), glycosidase inhibiton (A. Sirichai, S. Kasem, R. Sophon, P. Amom, N. Nattaya, C. Warinthom, D. Sujitra, Y. A. Sirintom, Bioorg. Med. Chem. Lett., 2004, 14, 2893), and steroidogenesis inhibition activities (S. Gobec, M. Sova, K. Kristan, T. L. Rizner, Bioorg. Med. Chem. Lett., 2004, 14, 3933). For example, 17b-hydroxysteroid dehydrogenases (17b-HSDs), involved in the synthesis of active 17b-hydroxy-forms (such as estradiol, testosterone, and dihydrotestosterone) using NAD(P)H or NAD(P) as cofactor, play a key role in hormonal regulation and function in the human and constitute emerging therapeutic targets for the control of estrogeno- and androgeno-sensitive diseases like breast cancer, endometrial cancer, prostate cancer, benign prostatic hyperplasia, acne, hair loss, etc. 17b-HSDs are implicated also in the development of polycystic kidney disease, pseudohermaphroditism, Zellweger syndrome and Alzheimer's disease ((a) J. Adamski, J. F. Jakob, Mol. Cell. Endocrinol., 2001, 171, 1; (b) H. Peltoketo, V. Luu-The, J. Simard, J. Adamski, J. Mol. Endocrinol., 1999, 23, 1). Similarly, α-glucosidase inhibitors have been shown to be potentially valuable for treatment of various diseases. These α-glucosidase inhibitors are known to be promising as anti-viral, anti-HIV agents, which alter glycosidation of envelope glycoprotein through interference with biosynthesis of N-linked oligosaccharides (P. B. Fischer, G. B. Karlsson, T. D. Butters, R. A. Dwek, F. M. J. Platt, Virol., 1996, 70, 7143; (b) B. D. Walker, M. Kowalski, W. C. Goh, K. Kozarsky, M. Krieger, C. Rosen, L. Rohrschneider, W. A. Haseltine, J. Sodroski, Proc. Natl. Acad. Sci. USA., 1987, 84, 8120). In addition, they have recently been used for treatment of B- and C type viral hepatitis (T. M. Block, X. Y. Lu, F. M. Platt, G. R. Foster, W. H. Gerlich, B. S. Blumberg, R. A. Dwek, Proc. Natl. Acad. Sci. U.S.A., 1994, 91, 2235). A number of cinnamic acids and esters have been reported to be active α-glucosidase inhibiting agents (S. Adisakwattana, K. Sookkongwaree, S. Roengsumran, A. Petsom, N. Ngamrojnavanich, W. Chavasiri, S. Deesamerc, S. Y. -Anuna, Bioorg. Med. Chem. Lett., 2004, 14, 2893).
Similarly, the higher esters of substituted cinnamic acids, particularly the octyl methoxy cinnamates, are well known sunscreen agents which possess high absorption in the 300-400 nm range and which are ideally suited for cosmetic applications since they are non-irritating to the skin and provide lubricity to prevent drying effects of wind and sun (A. Alexander, R. K. Chaudhari, U.S. Pat. No. 5,527,947, 1996). Moreover, cinnamic acids and cinnamates are used as a material for perfumes, as cinnamic aldehydes, cyclamen aldehyde, beta-amyl cinnamic aldehyde and the like.
There are a number of methods available for the synthesis of cinnamic esters as being discussed in detail in the prior art section. But all of the reported inventions suffer from expensive reagents, and substrates, low yields, long reaction periods, multi-steps approach, many bye-products, hazardous reagents and chemicals, all of which combinedly call for an improved method for the synthesis of cinnamic esters. In recent years, there has been a tremendous upsurge of interest in various chemical transformations mediated by reusable heterogeneous catalysts due to environmental and economical considerations ((a) P. Laszlo, Acc. Chem. Res., 1986, 19, 121; (b) S. V. Ley, I. R. Baxendale, R. N. Bream, P. S. Jackson, A. G. Leach, D. A. Longbottom, M. Nesi, J. S. Scott, R. J. Storter, S. J. Taylor, J. Chem. Soc., Perkin Trans. I, 2000, 3815; (c) R. Fricke, H. Hosslick, G. Lischke, M. Richter, Chem. Rev., 2000, 100, 2303. (d) R. Ballini, G. Bosica, R. Maggi, A. Mazzacani, P. Righi, G. Sartori, Synthesis, 2001, 12, 1826). Reactions assisted by heterogeneous catalysis have revolutionized the organic synthesis due to higher yields, easy work up and recyclability of the catalysts.
In our constant endeavor towards synthesis of important bioactive compounds ((a) A. K. Sinha, B. P. Joshi, R. Acharya, Chem. Lett., 2003, 32, 780; (b) A. Sharma, B. P. Joshi, A. K. Sinha, Bull. Chem. Soc. Jpn., 2004, 77, 2231; (c) V. Pathania, A. Sharma, A. K. Sinha, Helv. Chim. Acta, 2005, 88, 811), we were interested to develop conversion methodologies for commercially available economical cinnamaldehydes or cinnamyl alcohols into important bioactive cinnamates.
In this context, we, herein, disclose, a convenient and efficient green process for the preparation of various aryl or alkyl cinnamates under conventional, microwave and ultrasound directly from cinnamaldehydes or cinnamyl alcohols in the presence of an oxidizing agent, catalyst and an alcohol, with or without an organic solvent.

Single step green process for the preparation of substituted cinnamic esters with

Council of Scientific & Industrial Research


An improved method and resulting structures for producing a layered capacitor structure of memory cell of a DRAM device wherein a doped polysilicon spacer operates as a dopant source for an overlying polysilicon layer on the vertical and sharply inclined surfaces.

1. Field of the Invention
The present invention relates generally to dynamic random access memory devices, and more specifically to improvements in producing a layered capacitor structure for a random access memory cell.
2. Description of the Prior Art
As is well known, a memory cell used in a dynamic random access memory device (DRAM), is composed of a memory cell capacitor, such as a stacked capacitor, and a transfer transistor. In order to reduce the cost, and increase the speed of operation, the memory devices have become increasingly more miniaturized. In order to achieve this, each memory cell must occupy less space on the device. However, the cell capacitor must have roughly the same capacitance. The capacitance of a capacitor is proportional to the area of the electrodes. Thus, in order to maintain the capacitance level as the allotted area on the device becomes smaller, various new types of capacitors have been introduced, such as trench capacitors, stacked capacitors and similar devices.
U.S. Pat. No. 4,910,566 discloses an improved cell capacitor for a DRAM cell. In general, the patent discloses a memory cell capacitor consisting of a plate shaped film and a vertical projection film which are formed of doped polysilicon. The plate-shaped film and vertical projection film are formed on an interlayer insulation film. The vertical projection film is in contact with a sidewall of the plate-shaped film. With the vertical projection film, it is possible to increase the capacitance of the memory cell capacitance.
FIGS. 1 and 2 depict the general nature of the capacitor known in the prior art. In FIG. 2, a transfer transistor is shown consisting of a source 10 and drain 12, and a gate electrode 14. An insulating film 16 extends over the gate electrode. Opposite the transistor is shown a thick field oxide 18, and a gate electrode 20 of an adjacent memory cell, with an overlying insulating film 16. Positioned between the electrodes 14 and 20 is the cell capacitor consisting of a polysilicon layer formed of a horizontal plate portion 22 joined to a vertical projection portion 24. A thin insulation layer 26 overlays the cell capacitor.
The cell capacitor of U.S. Pat. No. 4,910,566 suffers from very serious shortcomings in that fabrication, as described, requires a very precise mask adjustment to form the opening over the drain region. Particularly for deep submicron technology, the tight control requirement of this patent will be more critical in order to keep the proper alignment. Also the concentrations of the dopant in the vertical projection portions 24 is low due to the limitation of ion implantation.

Layered capacitor structure for a dynamic random access memory device

Industrial Technology Research Institute


A globular illuminant device includes a hemispherical carrier, a circuit layer, a plurality of LED dies, an enclosure resin, and a hemispherical cover. The hemispherical carrier includes a carrying surface, a first cambered surface, and a first protrusion including a first surface. The circuit layer is placed on the first surface and the carrying surface. The LED dies are electrically connected to the circuit layer. The enclosure resin covers the LED dies. The hemispherical cover includes a joining surface, a second cambered surface, and a recess formed on the joining surface and concave toward second cambered surface. The hemispherical cover is assembled with the hemispherical carrier such that the joining surface is in contacted with the carrying surface while the LED dies and the enclosure resin are disposed within the recess.

1. Field of the Invention
The present invention relates to an illuminant device, and in particular to a globular illuminant device.
2. Description of Related Art
A light emitting diode (LED) is a kind of semiconductor device, which exploits the property of direct-bandgap semiconductor material to convert electric energy into light energy efficiently and has the advantages of long service time, high stability and low power consumption and is developed to replace the traditional non-directivity light tube and incandescent lamp.
The LED is a point-like light source and has high directivity so that the lighting surface of the LED is narrower than that of the traditional light sources, and the luminous intensity of the LED is gradually reduced while the lighting distance is increased, so that the LED is more suitable for providing short-distance and small area lighting fixture, such as table lamp.
In order to solve the mentioned problem, many manufacturers assemble and arrange multiple LEDs to centralize light for solving the problem of narrow angular lighting range. However, the required power for driving the LEDs is increased when the number of the LEDs is increased, therefore, the effect of saving energy cannot be achieved. Moreover, the price of LED lamp is far higher than the traditional light source so as to reduce the will of using LED lamp.


A ship is provided with microbubble generators attached below the waterline to supply microbubbles, which decrease the ship's frictional resistance during navigation and improve fuel efficiency. The below waterline region (L.W.L.) of the ship is divided into an upper region (R1) proximate the waterline, and a lower region (R2) proximate the ship's bottom. The air supply to the microbubble generators (10) in the upper region (R1) is performed through a pipe (3), one end of which is exposed to the atmosphere. The air supply to the microbubble generators (10) in the lower region (R2) is performed through a branch pipe (6) from a pipe (5) using an assist compressor (4), which is arranged as a closed system instead of being exposed to the atmosphere.

It is known in the art that a ship's hull friction resistances in water will decrease by supplying air bubbles to the surface of a moving hull a1.
There are two types of means to send air to the bubble generator prepared in the ship hull's bottom (lateral surface); one type is a closed type which depresses the air-liquid interfaces in an air charging line to an air bubbles genesis region by means of a compressor; and a second type is an open type system that depresses the air-liquid interface in an air charging line to an air bubbles generator region by negative pressure.
Prior art document 1 (JP 2008-120246 A) and prior art document 2 (JP 2008-143345 A) describe a closed type system. Prior art 1 describes a structure which attaches a flat board so that it covers an air hole, and Prior art 2 describes the structure which introduces air into the water in a uniform state, attaching a baffle plate which covers gas pressure jets.
Here, the flat board described in Prior Art 1 and the baffle plate described in Prior Art 2 do not generate negative pressure as described in the documents concerned.
The closed type forcedly spouts air and as a result the air bubbles will inevitably become large. In order to effectively reduce frictional resistance, air bubbles must stay on the surface of hull for a long time. For this reason it is required that the bubble diameter should be as small as possible. Prior Art 3 (JP 2002-2582 A) describes that such microbubbles are generated according to the Kelvin-Helmholtz-Instability phenomenon.
Namely, in Prior art 3 in the panels of the ship's bottom (submerged surface) a recess is installed. This recess is connected together with a gas inlet tube to supply air to the recess and has a wedge-shaped negative pressure formation part attached to the upper stream side of the recess, which causes the Kelvin-Helmholtz-Instability phenomenon to make microbubble in the recess. Moreover, in Prior art 4 (JP 4070385), the technology of employing a wing is disclosed as a means which makes microbubbles instead of the wedge-shaped negative pressure formation part of Prior art 3.
[Prior art 1] Laid Open Patent JP2008-120246A
[Prior art 2] Laid Open Patent JP2008-143345A
[Prior art 3] Laid Open Patent JP2002-2582A
[Prior art 4] U.S. Pat. No. 4,070,385

Frictional resistance reduction ship and operation method


A cutting element having a substrate, an abrasive layer mounted to the substrate at an interface, and a longitudinal axis extending through the abrasive layer and the substrate is disclosed, wherein the substrate has a binder material, a plurality of metal carbide grains bonded together by an amount of the binder material, and at least one binder gradient, and wherein the amount of binder material decreases along at least one direction to form the at least one binder gradient.

1. Field of the Invention
Embodiments disclosed herein relate generally to cutting elements for drilling earth formations. More specifically, embodiments disclosed herein relate to cutting elements containing metal carbide substrates.
2. Background Art
In a typical drilling operation, a drill bit is rotated while being advanced into a soil or rock formation. The formation is cut by cutting elements on the drill bit, and the cuttings are flushed from the borehole by the circulation of drilling fluid that is pumped down through the drill string and flows back toward the top of the borehole in the annulus between the drill string and the borehole wall. The drilling fluid is delivered to the drill bit through a passage in the drill stem and is ejected outwardly through nozzles in the cutting face of the drill bit. The ejected drilling fluid is directed outwardly through the nozzles at high speed to aid in cutting, flush the cuttings and cool the cutter elements.
There are several types of drill bits, including roller cone bits, hammer bits and drag bits. Roller cone rock bits include a bit body adapted to be coupled to a rotatable drill string and include at least one "cone" that is rotatably mounted to a cantilevered shaft or journal as frequently referred to in the art. Each roller cone in turn supports a plurality of cutting elements that cut and/or crush the wall or floor of the borehole and thus advance the bit. The cutting elements, either inserts or milled teeth, contact with the formation during drilling. Hammer bits typically include a one piece body with having crown. The crown includes inserts pressed therein for being cyclically "hammered" and rotated against the earth formation being drilled.
Drag bits, often referred to as "fixed cutter drill bits," include bits that have cutting elements attached to the bit body, which may be a steel bit body or a matrix bit body formed from a matrix material such as tungsten carbide surrounded by a binder material. Drag bits may generally be defined as bits that have no moving parts. However, there are different types and methods of forming drag bits that are known in the art. For example, drag bits having abrasive material, such as diamond, impregnated into the surface of the material which forms the bit body are commonly referred to as "impreg" bits. Drag bits having cutting elements made of an ultra hard cutting surface layer or "table" (typically made of polycrystalline diamond material or polycrystalline boron nitride material) deposited onto or otherwise bonded to a substrate are known in the art as polycrystalline diamond compact ("PDC") bits, or more broadly as shear cutter bits. Shear cutter bits drill soft formations easily, but they are frequently used to drill moderately hard or abrasive formations. They cut rock formations with a shearing action using small cutting elements referred to as shear cutters that do not penetrate deeply into the formation. Because the penetration depth is shallow, high rates of penetration are achieved through relatively high bit rotational velocities.
An example of a shear cutter bit is shown in FIG. 1. FIG. 1 shows a rotary drill bit 10 includes a bit body 12 having a cutting end 11 and a threaded pin end 13 for connection to a drill string (not shown). The cutting end 11 of the bit body 12 is formed with a plurality of blades 14, which extend generally outwardly away from a central longitudinal axis of rotation 16 of the drill bit. A plurality of shear cutters 18 having a cutting layer 19 bonded to a carbide substrate 17 are disposed side by side along the length of each blade. The number of shear cutters 18 carried by each blade may vary. The shear cutters are positioned along the leading edges of the bit body blades so that as the bit body is rotated, the shear cutters engage and drill the earth formation. In use, high forces may be exerted on the shear cutters, particularly in the forward-to-rear direction. Additionally, the bit and the shear cutters may be subjected to substantial abrasive forces. In some instances, impact, vibration and erosive forces have caused drill bit failure due to loss of one or more cutters, or due to breakage of the blades.
In a typical shear cutter, a compact of polycrystalline diamond ("PCD") (or other superhard material, such as polycrystalline cubic boron nitride) is bonded to a substrate material, which is typically a sintered metal-carbide, to form a cutting structure. A PCD shear cutter may be formed by placing a mixture of diamond grains or diamond grains and catalyst material on a substrate and subjecting the assembly to high pressure, high temperature ("HPHT") conditions. Alternatively, a pre-formed diamond table may be placed on a substrate and subjected to HPHT conditions to bond the diamond table to the substrate. During the HPHT process, metal binder migrates from the substrate and passes through the diamond grains to promote intercrystalline growth between the diamond grains, binding the diamond grains to each other and binding the formed PCD table to the substrate. In particular, PCD refers to a polycrystalline mass of diamond grains or crystals that are bonded together to form an integral, tough, high-strength mass or lattice. The resulting PCD structure produces enhanced properties of wear resistance and hardness, making PCD materials extremely useful in aggressive wear and cutting applications where high levels of wear resistance and hardness are desired.
Shear cutter substrates are commonly formed from a carbide/metal composite (often referred to as a cermet), which includes hard particles of carbide surrounded by a metal binder, typically cobalt, which acts as a matrix. The individual hard particles thus are embedded in a matrix of a relatively ductile metal such that the ductile metal matrix provides the necessary toughness, while the grains of hard material in the matrix furnish the necessary wear resistance. The ductile metal matrix also reduces crack formation and suppresses crack propagation through the composite material once a crack has been initiated.
Due to its toughness and high wear resistance, cemented tungsten carbide is a common cermet that is used to form cutting element substrates in rock-drilling and earth boring applications. "Cemented tungsten carbide" generally refers to a tungsten carbide composite which comprises tungsten carbide ("WC") grains bonded together by a binder phase. Among the types of tungsten carbide particles that may be used to form a cemented tungsten carbide, for example, include cast tungsten carbide, macro-crystalline tungsten carbide, carburized tungsten carbide and cemented tungsten carbide. In most applications, the binder phase comprises cobalt (Co), nickel (Ni), and/or iron (Fe). However, tungsten carbide grains dispersed in a cobalt binder matrix is the most common form of cemented tungsten carbide currently used for cutting elements in drilling applications, and is typically classified by grades based on the grain size of the tungsten carbide particles used and the cobalt content. However, in some cases, cemented tungsten carbide may be classified by grades based on the cobalt content and a material property such as hardness or wear resistance.
FIG. 2 illustrates the conventional microstructure of a tungsten carbide/metal composite. As shown in FIG. 2, cemented tungsten carbide 20 includes tungsten carbide grains 22 that are bonded to one another by a metal binder phase 24. As illustrated, tungsten carbide grains may be bonded to other grains of tungsten carbide (depending on the metal content), thereby having a tungsten carbide/tungsten carbide interface 26, and/or may be bonded to the metal phase, thereby having a tungsten carbide/metal interface 25. The unique properties of tungsten carbide cermets result from this combination of hard carbide particles with a tougher, ductile metal phase.
In conventional carbide cermets, it is possible to increase the toughness of the composite by increasing the amount of metal binder present in the composite and/or by increasing the carbide grain size. Conversely, the hardness of the carbide cermet may be increased by decreasing the amount of metal binder and/or by decreasing the carbide grain size. Thus, toughness and hardness are inversely related. To utilize both characteristics of toughness and hardness, some prior art cermets have been designed to have areas with higher amounts of binder (increased toughness) and areas with lower amounts of binder (increased hardness) by forming a binder gradient.
For example, U.S. Pat. Nos. 7,699,904 and 7,569,179, which are incorporated herein by reference, describe methods of forming functionally graded materials having a metal matrix phase, such as cobalt, and a hard phase made of at least two chemical elements, such as tungsten and carbon. The functionally graded composites have a continuous gradient of the metal matrix phase that is formed by designing an initial (non-continuous) gradient of one of the chemical elements of the hard phase and then liquid phase sintering the hard phase and metal matrix phase. For example, an initial gradient for tungsten carbide may be formed by creating a first layer deficient in carbon and a second layer enriched with carbon. When the tungsten carbide layers are sintered with the metal matrix phase, the heated conditions cause the carbon atoms to diffuse in a direction from the enriched layer to the deficient layer and atoms of the metal matrix to flow in the same direction as the diffusion.
Other prior art methods of forming continuous gradient of the matrix metal phase may include, for example, creating a graded structure by using two layers with different magnetic saturation numbers, as described in U.S. Pat. No. 5,541,006, and creating a graded structure through a carburizing treatment, as described in U.S. Pat. No. 6,896,460. However, such methods have limitations with respect to the size of gradient that may be formed. In particular, gradients formed using different magnetic saturation may be limited to a metal matrix gradient having only 1-2% difference, and gradients formed by carburization treatments may be limited to small depths of the gradient, as measured from the surface of the treated composite. Also, this process requires formation of an eta (η) phase (i.e., a complex carbide compound of tungsten, cobalt, and carbon), which has been known in the art as forming brittle grains around WC crystals, and thus, sites for crack initiation and propagation. Thus, this prior art gradient-forming method requires forming a hard phase element deficient layer and a hard phase element enriched layer in order to create a continuous gradient of the matrix metal phase.
Moreover, it has not yet been known to use graded carbides such as the ones described above in a shear cutter substrate, which undergoes HPHT processing to attach an ultra-hard cutting layer to the substrate. Accordingly, there is a need for improved cutting element substrates that have properties of both increased toughness and increased hardness and that may be bonded to an ultra-hard cutting table.

Shear cutter with improved wear resistance of WC-CO substrate


A metal oxide semiconductor field effect transistor (MOSFET) includes a semiconductor substrate and a interlayer dielectric (ILD) over the semiconductor substrate. A gate structure is formed within the ILD and disposed on the semiconductor substrate, wherein the gate structure includes a high-k dielectric material layer and a metal gate stack. One or more portions of a protection layer are formed over the gate stack, and a contact etch stop layer is formed over the ILD and over the one or more portions of the protection layer. The metal gate stack includes aluminum and the protection layer includes aluminum oxide.

In advanced technology nodes of integrated circuit industry, high k dielectric material and metal are adopted to form a gate stack of a field-effect transistor (FET) such as a metal-oxide-semiconductor field-effect transistors (MOSFETs). Metal gate stacks are often planarized, such as by chemical-mechanical polishing (CMP), and then covered with a contact etch-stop layer (CESL). Additional processing operations are then performed, including forming an interlayer dielectric (ILD) above the metal gate stack, and then patterning and forming a contact through the ILD. As a result of these additional processing operations, it has been found that damage sometimes occurs to the metal gate stacks. For example, an acid solvent can reach the metal gate stack and adversely affect the gate stack, such as by forming a void or other defect. It is desired to maintain the integrity of the metal gate stack throughout the various processes.
It is also desired to maintain high production efficiency, adding to maintain or reduce the number of processing operations and processing tools used to fabricate devices such as MOSFETs. Therefore, an improved interface for a metal gate stack and a method making the same are needed to address the issues identified above.

Taiwan Semiconductor Manufacturing Company, Ltd.


A first phase comparator 22 of digital type and a second phase comparator 32 of sampling type are provided. Near a lock phase, an output current Iout2 is fed from the second phase comparator 32 to a voltage-controlled oscillator 14 through a change-over switch 40. In other phases, an output current Iout1 is fed thereto from the first phase comparator 22. When a reference signal fs is missing, a complementing circuit 50 complements a pulse to at least the reference signal fs input to the first phase comparator 22. A noise detecting/removing circuit 60 detects and removes noise from the reference signals fs, permits the reference signals fs to be fed to the first and second phase comparators 22 and 23, and halts the operations of the two phase comparators 22 and 32 for only a predetermined period of time after the noise has been detected. Therefore, the PLL circuit stably operates and characters are clearly displayed on a screen even when the noise is contained in the horizontal synchronizing signals of the video signals or even when the signals are missing.

1. Field of the Invention
The present invention relates to a technology that can be particularly effectively adapted to an integrated circuit device and to a PLL circuit. More particularly, the invention relates to a technology that can be effectively utilized for a device for generating clock signals for controlling the character display positions at the time of adding character data to an image such as of TV, and or can be effectively utilized for a device for generating clock signals necessary for the A/D (analog-to-digital) conversion of video signals.
2. Prior Art
There has been known a PLL (phase-locked loop) circuit which is a phase-synchronizing circuit that follows up the phase of an input signal (reference signal) that serves as a reference, comprising, as shown in FIG. 26, a phase comparator 12 which compares a reference signal fs input through a reference signal input terminal 11 with a signal (hereinafter referred to as to-be-compared signal) obtained by dividing an oscillation output signal fv of a voltage-controlled oscillator (VCO) 14 by a frequency divider 15, and generates a phase error signal corresponding to the difference in phase between the two signals fs and fd, a low-pass filter 13 which decreases high-frequency components of the phase error signal thereby to obtain an error signal voltage Vd, a voltage-controlled oscillator 14 which, upon receiving the error signal voltage Vd, varies the frequency of the oscillation output signals fv so that the frequency difference from the reference signal fs decreases, and a frequency divider 15, the signals divided by the frequency divider 15 being fed back to the phase comparator 12. In FIG. 26, reference numeral 16 denotes an output terminal of the voltage-controlled oscillator 14.
The phase comparator 12 may often be of the digital type called phase/frequency comparator (frequency/phase detector circuit) in which the polarity of a phase error signal of when the frequency is deviated and the polarity of a phase error signal after the frequency is brought into agreement continuously operate.
As the PLL circuits using two phase comparators, furthermore, there have been known a circuit which uses a memory-type phase comparator at the time of establishing synchronism such as of communications and changes it to a zero-memory phase comparator near the lock-in (Japanese Patent Publication No. 70124/1990), a circuit which effects the sweeping with a digital phase/frequency comparator from the initial state to the pull-in range and, then, changes it to an analog phase comparator (Japanese Patent Publication No. 149018/1990), and a circuit which adds up the output of a first phase comparator and the output of a second phase comparator supplied with an inverted input signal (Japanese Patent Laid-Open No. 165226/1989).
It was, however, found out by the present inventors that the PLL circuits using the digital phase comparator shown in FIG. 26 involve a problem described below.
That is, in a PLL circuit using a conventional digital phase comparator, there exists a blind region near the lock phase where the phase difference becomes 0.degree. as shown in FIG. 27 due to the frequency characteristics of phase error signals of an output circuit. Therefore, a very small phase error signal is not actually output that should be output near the lock phase. Accordingly, the oscillation output signal fv of the voltage-controlled oscillator 14 includes jitter and lose stability.
Furthermore, the digital phase comparator detects the phase difference between the pulse edges of the two signals. Therefore, when the synchronizing signals are input as reference signals fs to the phase comparator 12 creating a state that a pulse, that should be input, is missing and is not input like during a special reproduction of a VTR (video tape recorder) (this state will be hereinafter referred to as loss of signal), incorrect phase error signals (output current Iout of FIG. 28) are continuously output as shown in FIG. 28 until the phase of the to-be-compared signal fd is brought into agreement with the phase of the reference signal fs. Noise is often superposed on the synchronizing signals during the special reproduction of VTR. Even when the synchronizing signals on which the noise is superposed are used as reference signals fs for the phase comparator 12, incorrect phase error signals (output current Iout of FIG. 29) are continuously output as shown in FIG. 29 until the phase of the to-be-compared signal fd is brought into agreement with the phase of the reference signal fs. The loss of signal and the noise cause disturbance in the operation of the voltage-controlled oscillator 14 that generates clock signals for controlling the character display positions at the time of adding character data to an image, permitting the displayed characters to oscillate.
The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a PLL circuit that is capable of stably producing output signals without affected by jitter caused by a blind region of the phase comparator.
Another object of the present invention is to provide a PLL circuit which stably operates without affected by the missing of signal or noise.
The above and other objects as well as novel features of the present invention will become obvious from the description of the specification and the accompanying drawings.

Phase locked loop circuit and a picture reproducing device


A second group of drive voltages V3 to V5 has a voltage range that is separate from, and does not overlap a first group of drive voltages V0 to V2. The first group of drive voltages V0 to V2 is supplied from first power sources VDD and VSS through operational amplifiers OP1 and OP2. The second group of drive voltages V3 to V5 is set with reference to VEE, and is supplied from the first power sources VDD and VSS through the operational amplifiers OP1 and OP2. Voltage conversion capacitors C11 and C12 are charged by turning on and off a first group of switches SW11 to SW13, and are discharged by turning on and off a second group of switches SW14 to SW16, thus causing the output of the second group of drive voltages V3 to V5 which have references to VEE.

1. Technical Field
This invention relates to a power circuit, a liquid crystal display device incorporating this power circuit, and electronic equipment incorporating either the power circuit or the liquid crystal display device.
2. Related Art
FIG. 18 is a schematic diagram of electrodes of a liquid crystal panel that is multiplex driven. To simplify the description, this liquid crystal panel includes nine segment electrodes and six common electrodes. Each rectangle in this figure represents an electrode formed in the liquid crystal panel, and these electrodes are divided into segment electrodes (SEG1 to SEG9) and common electrodes (COM1 to COM6), depending on the signals that are applied thereto. The square shaded portion at each intersection of electrodes represents a display dot. To ensure that each display dot operates as a capacitor, a capacitor links the segment electrode and common electrode at a corresponding display dot.
Voltage levels V0 to V5 that are necessary for driving liquid crystal elements by a multiplex-driven method with a high duty ratio (six-level drive method) generally satisfy the relationships V0-V1=V1-V2 =V3-V4=V4-V5 and V0>V1>V2>V3>V4>V5, as shown in FIG. 19. In this case, it is assumed that V0 to V2 are a first group of drive voltages and V3 to V5 are a second group of drive voltages. The voltage range of the first group of drive voltages V0 to V2 does not overlap the voltage range of the second group of drive voltages V3 to V5, and is separate therefrom.
FIG. 19 shows examples of signal waveforms applied to the segment and common electrodes. The signal applied to a segment electrode generally switches between voltage levels V3 and V5 during the period of a frame 0 (hereinafter called FR0). Similarly, the signal switches between voltage levels V0 and V2 during the period of a frame 1 (hereinafter called FR1). This switching of the voltage level at the segment electrode depends on the pattern to be displayed.
At the same time, the signal applied to a common electrode is at voltage level V4 during a non-selected state in the FR0 period, or at voltage level V0 during a selected state. Similarly, the signal is at voltage level V1 during the non-selected state in the FR1 period, or at voltage level V5 during the selected state. The period during which a common electrode is in the selected state differs for all of the common electrodes, and it is not possible for a plurality of common electrodes to be simultaneously selected. Voltage levels are inverted between the FR0 and the FR1 periods, to drive the liquid crystal in an alternating fashion.
The switching of the voltage levels at the segment and common electrodes is in accordance with the charging and discharging of capacitances existing within the liquid crystal panel. This means that currents flow through the liquid crystal panel between each of the voltage levels V0 to V5. These currents are hereinafter called panel currents.
The voltage level of each segment electrode switches between V0 and V2 (in the FR1 period) or V3 and V5 (in the FR0 period). For a large proportion of the time, each common electrode is in a non-selected state, so the voltage level thereof is mostly at V1 (in the FR1 period) and at V4 (in the FR0 period). This means that a panel current caused by a switch in voltage level at a segment electrode (hereinafter called a segment panel current) flows mainly between the first group of drive voltages V0, V1, and V2 or the second group of drive voltages V3, V4 and V5. Similarly, a panel current caused by a switch in voltage level at a common electrode (hereinafter called a common panel current) flows mainly between V5 and a voltage within the first group of drive voltages V0, V1, and V2, or between V0 and a voltage within the second group of drive voltages V3, V4, and V5.
A power circuit that supplies the above panel currents is disclosed as a prior-art method in Japanese Patent Application Laid-Open No. 2-150819. The configuration thereof is shown in FIG. 20. In this figure, external power sources VDD and VEE are provided to drive the power circuit, where VDD is greater than VEE. Divided voltage levels V1' to V4' are generated between VDD and VEE by series-connected resistors R1 to R5. These divided voltage levels are input to operational amplifiers OP1 to OP4 that are each connected in a voltage-follower configuration. The operational amplifiers OP1 to OP4 use VDD and VEE as power sources to convert V1' to V4' by lowering the high impedances thereof. C1 to C4 denote smoothing capacitors that control variations in the output voltage levels V1 to V4 of the operational amplifiers OP1 to OP4. Resistors R8 to R11 limit the output currents of the operational amplifiers OP1 to OP4, and thus reduce the power consumption thereof.
However, this prior-art method has problems, as described below.
The first problem with this prior-art method concerns the way in which a large amount of power is wasted when panel currents are supplied. The reason for this is as follows. When a liquid crystal panel is driven using this power circuit, panel currents are supplied as part of the current flowing from VDD to VEE. Consider, for example, a segment panel current flowing from voltage level V3 to V4. This segment panel current flows out initially from the power source VDD and into the liquid crystal panel through the operational amplifier OP3, as shown in FIG. 21. This current from the liquid crystal panel flows into the power source VEE through the operational amplifier OP4. When a segment panel current is supplied in this fashion from voltage level V3 to V4, the current flowing from VDD to V3 causes the operational amplifier OP3 to generate heat. Similarly, the current flowing from V4 to VEE causes the operational amplifier OP4 to generate heat. In other words, these currents do not operate efficiently in the driving of the liquid crystal panel. All the other panel currents are equally inefficient. This means that the use of the power circuit of FIG. 20 for supplying the common panel currents and segment panel currents leads to wasteful consumption of power as heat generation of the operational amplifiers. In this particular example, the common panel currents mainly flow between V5 and a voltage within the first group of drive voltages V0, V1 and V2, or between V0 and a voltage within the second group of drive voltages V3, V4 and V5. Therefore, there is a large voltage difference between the voltage levels that these currents flow between, and there is only a small difference between these voltages and the voltage between the power sources VDD and VEE. In contrast, the segment panel currents mainly flow between voltages within the first group of drive voltages V0, V1 and V2, or between voltages within the second group of drive voltages V3, V4 and V5. Therefore, there is a small voltage difference between the voltage levels that these currents flow between, and there is a large difference between these voltages and the voltage between the power sources VDD and VEE. Thus it is clear that the proportion of power that is wasted by such components as the operational amplifiers is greater, when supplying a segment panel current than supplying a common panel current. In other words, in order to prevent such waste of power, it is necessary to improve the method used to supply segment panel currents.
The second problem with this prior-art method concerns the large power consumption caused by idling currents in the operational amplifiers. In other words, the operational amplifiers OP1 to OP4 of the prior art are driven by the power sources VDD and VEE, as shown in FIG. 20. However, since these power sources VDD and VEE are also used as power sources for generating the drive voltages for the liquid crystal panel, the voltage between VDD and VEE is extremely large. For a constant current, power consumption is proportional to voltage. Therefore, if the voltage between VDD and VEE increases, the power wasted by the idling currents in the operational amplifiers OP1 to OP4 also increases.
The third problem with this prior-art method concerns the way in which the above described use of power sources VDD and VEE with a large voltage difference therebetween requires expensive operational amplifiers that can withstand such high voltages.
To design a liquid crystal display device with a higher duty ratio, it is generally necessary to increase the voltage between the power sources VDD and VEE even further. This would further aggravate the above described three problems.
Note that another prior-art method for a power circuit that supplies power to a liquid crystal panel is disclosed in Japanese Patent Application Laid-Open No. 3-200214, whereby a switched capacitor circuit is used to generate voltage level V5 from V1 and voltage level V4 from V2. However, this prior-art method has the objectives of reducing the number of operational amplifiers or the amount of wiring between the power circuit and the liquid crystal panel for implementing a smaller device. Nevertheless, the prior art does not have the objective of reducing the power consumption, unlike the present invention.
In addition, this prior-art method has a five-level output wherein the voltage of a common electrode when it is not selected is the same (V3=GND) before and after each polarity inversion, in other words, during the FR0 and FR1 periods of FIG. 22(A). In order to increase duty ratio for driving the liquid crystal with this power source configuration, it is necessary to increase the voltages between V1 and V3 and between V3 and V5, as shown in FIG. 22(B). This causes a problem in that it requires provision of a high-voltage-withstanding driver chip for driving the liquid crystal. Therefore, the power source configuration of FIG. 22(B) is generally used, when a liquid crystal device is to be driven at a low duty ratio. The power source configuration shown in FIG. 22(C) has been proposed for driving a liquid crystal device at a high duty ratio, to solve the problem generated by the power source configuration of FIG. 22(B). This method is generally used to drive a liquid crystal device at a high duty ratio. The present invention is aimed at the power source configuration shown in FIG. 22(C), but its objectives and configuration are different from those of the prior-art method that is designed for the power source configuration shown in FIG. 22(B).
The present invention is devised to resolve the above described technical concerns, and has as its objective the provision of an inexpensive, less power-consumption power circuit, liquid crystal display device and electronic equipment.

Power circuit, liquid crystal display device and electronic equipment


A seating tool 10 for installing connectors on a circuit board comprises a base plate 12, an alignment plate 40 and fasteners 60 to fasten them together at respective fastening locations. The alignment plate 40 has at least two connector alignment surfaces 42, 44 at different locations thereon and a set of at least two fastening locations 46, 48 associated with a respective alignment surface for securing the alignment plate 40 to the base plate 12 in at least two orientations relative to the base plate 12 to accommodate board-mounting of differing connectors having different dimensions of the posts from the front faces of the connectors.

When mounting electrical connectors to a substrate such as a printed circuit board "PCB", it is important that the board engaging posts of electrical terminals are precisely aligned with the corresponding through holes of the substrate. In some applications it is desirable to use terminals having compliant sections that are able to both mechanically secure the connector to the substrate and electrically connect the terminals therein to plated through-holes of the substrate without the need for solder. Mounting a vertically oriented electrical connector is relatively straight forward as tools can be used to apply pressure directly against the mating face of the connector or in some instances specialized tools are used to apply force directly to each of the terminals. Additional problems arise when mounting right angle connectors to a substrate, such as a circuit board, because the board mounting posts are offset from the mating face of the connector such that the insertion force must be exerted on the horizontally extending terminal portions above the compliant posts in a manner to ensure that compliant posts remain perpendicular to the through-holes as they are inserted into the board. Care needs to be taken not to apply pressure at the portion of the housing that extends laterally beyond the axes of the compliant posts causing the connector to tip and the compliant post to either bend or engage the through-holes at an acute angle. It is important, therefore, that the forward portion of the connector housing remain parallel to the mounting substrate during the assembly process.

Seating tool for installing electrical connectors to printed circuit boards


A device for milling and/or lathing workpieces including at least one machine bed, on which there is at least one tool holder and one workpiece spindle as part of a workpiece holder with an axis of rotation, whereby the tool holder has at least one tool drive with an axis of oscillation running parallel to the axis of rotation, whereby the workpiece holder and the tool holder can travel relative to each other in the direction of an axis of translation that runs at a right angle to the axis of oscillation. The workpiece holder has a linear drive that can travel in the direction of the axis of translation.

European Patent Application EP 1 323 497 A3 discloses a machine for the production of optically active surfaces with an electronically speed-controlled workpiece receptacle that can be rotated around a C-axis and that has a tool carriage which, relative to the C-axis, can move in the radial direction of an X-axis and in the axial direction of a Z-axis. Here, for the axial feed movement, there is a linear motor and for the X-, Z- and C-axes, there is a control processor that controls the position of the Z-axis, the position of the X-axis as well as the rotation of the C-axis. In addition, the axes are arranged essentially vertically or else they span a vertical machining plane. In addition to the axis of translation x, the tool receptacle also has the oscillating axis z.