The present invention describes a method or uses of prevention and/or treatment of a cancer or a tumor, and in particular to a combination therapy, methods, compositions and pharmaceutical packages comprising an inhibitor of receptors of the EGFR family or a chemotherapeutically active pyrimidine analogue and certain platinum-based chemotherapeutic agents.

Platinum compounds are among the most active chemotherapeutic agents available for the treatment of a variety of cancers and tumors. The use of some of these compounds, e.g., cisplatin, is restricted by both toxological and resistance considerations. To overcome these issues, efforts were started to discover novel platinum compounds which do not share certain properties of cisplatin. One compound that was identified is satraplatin (JM216), a platinum (Pt) IV complex. Satraplatin (JM216) was selected for clinical development because of several advantageous properties: (a) high cytotoxic activity in vitro against several solid tumor cell lines, including cisplatin-resistant ones; (b) in vivo antitumor activity against a variety of murine- and human-xenograft tumor models; (c) a relatively mild toxicity profile (such as the absence of kidney toxicity and neurotoxicity), and (d) oral availability.
In Phase 2 clinical trials, satraplatin showed activity against several different cancers, including prostate, ovarian, and small cell lung (SCL) cancers. In a Phase II-III clinical trial in Hormone Refractory Prostate Carcinoma (HRPC) patients, the combination of satraplatin plus prednisone was more active than prednisone alone (ASCO meeting, 2003; Sternberg et al., Oncology (2005) 68, 2). Satraplatin is currently undergoing Phase 3 development in a worldwide registration clinical study evaluating satraplatin plus prednisone versus placebo plus prednisone as second-line cytotoxic chemotherapeutic treatment against hormone refractory prostate cancer. Recently it was reported that the study data show that the results for progression-free survival (PFS) are highly statistically significant (p<0.00001) using the protocol-specified log-rank test. Patients who received satraplatin plus prednisone had a 40% reduction in the risk of disease progression (hazard ratio of 0.6; 95% Confidence Interval: 0.5-0.7) compared with patients who received prednisone plus placebo. The improvement seen in progression-free survival by patients treated with satraplatin increased over time. Progression-free survival at the median (50th percentile) demonstrated a 13% improvement in patients who received satraplatin plus prednisone (11 weeks) compared to patients who received prednisone plus placebo (9.7 weeks). Progression-free survival at the 75th percentile showed an 89% improvement for patients in the satraplatin arm (36 weeks) versus patients in the placebo arm (19 weeks). At 6 months, 30% of patients in the satraplatin arm had not progressed, compared to 17% of patients in the control arm. At 12 months, 16% of patients who received satraplatin had not progressed, compared to 7% of patients in the control arm. All of these analyses were conducted on an intent-to-treat basis. The current standard treatment of HRPC is primarily palliative and includes first line chemotherapeutic regimens with agents such as estramustine, mitoxantrone and taxanes, with docetaxel being increasingly used as a first-line chemotherapeutic agent.
Satraplatin is considerably different from other platinum agents, like e.g. cisplatin. Using a panel of ovarian cancer carcinoma cell lines Kelland et al. (Cancer Res (1992), 52, 822) demonstrated that satraplatin is significantly more cytotoxic than cisplatin, and that satraplatin exhibits selective cytotoxic effects against intrinsically cisplatin-resistant cell lines. Loh et al. (Br. J. Cancer (1992) 66, 1109) confirmed these findings. Loh et al. furthermore came to the conclusion that the increased accumulation of satraplatin, which is a result of its enhanced lipophilicity, accounts for the dramatic increase of the potency of satraplatin over cisplatin. Other studies reporting on the activity of satraplatin towards cell lines with acquired or intrinsic resistance to cisplatin are those of Mellish et al. (Br J Cancer (1993) 68, 240), using human cervical squamous cell carcinoma cell lines, and Orr et al. (Br J Cancer (1994) 70, 415), using murine leukaemia cell lines. In the latter report the cell lines used were not just resistant to cisplatin, but also to tetraplatin and carboplatin.
Furthermore, cisplatin was repeatedly shown not to be effective against prostate cancer. Qazi & Khandekar (Am J Clin Oncol (1983) 6, 203) demonstrated in a phase II trial that cisplatin is not effective in patients with metastatic prostatic carcinoma. Hasegawa et al. (Cancer & Chemother (1987) 14, 3279) reported that the range of effective dose was wider for other platinum agents like carboplatin than for cisplatin. Even in combination treatment, cisplatin-comprising regimens demonstrate limited activity, e.g. in combination with mitoxantrone in metastatic prostate cancer (Osborne et al., Eur J Cancer (1992) 28, 477). Therefore, cisplatin is not a substitute for satraplatin as an agent to be used in prostate cancer.
Twentyman et al. (Cancer Res (1992) 52, 5674) investigated the sensitivity of human lung cancer cell lines with acquired or inherent resistance to cisplatin, to a series of novel platinum compounds, including satraplatin. In this study, cisplatin and carboplatin were found to act very similar, whereas satraplatin did not.
In spite of different routes of administration Kelland et al. (Int J Oncol (1993) 2, 1043) demonstrated the surprising finding that the efficacy of orally administered satraplatin is comparable to that of cisplatin and carboplatin administered intravenously, as determined in human ovarian carcinoma xenograft models. These findings were confirmed by Rose et al. (Cancer Chemother Pharmacol (1993) 32, 197), using murine and human tumor models. McKeage et al. (Cancer Res (1994) 54, 4118) investigated the differences of the schedule dependencies associated with these routes of administration.
In another study by Kelland et al. (Cancer Res (1993) 53, 2581) many of the above mentioned differences between satraplatin and cisplatin were confirmed. Furthermore it was found, that the cytotoxicity of satraplatin was dependent on the time of drug exposure. Again, it was confirmed that satraplatin does not exhibit cross resistance to cisplatin, whereas other platinum agents, e.g. tetraplatin, do. Without being bound to any particular theory, satraplatin circumvents transport-determined acquired resistance to cisplatin.
Mellish et al. (Cancer Res (1994) 54, 6194) investigated the mechanisms of acquired resistance to satraplatin in two human ovarian carcinoma cell lines. They found that, in contrast to cisplatin, acquired resistance to satraplatin is not mediated through reduced drug accumulation, but by increased intracellular GSH levels or increased DNA repair.
Sharp et al. (Clin Cancer Res (1995) 1, 981) compared the transport of cisplatin and satraplatin in human ovarian carcinoma cell lines. Cisplatin transport in the parental cell lines occurs via passive diffusion and active/facilitated transport, whereas in a cisplatin-resistant cell lines cisplatin enters cells by passive diffusion only. Without being bound to any particular theory, satraplatin circumvents cisplatin resistance by increasing the drug uptake. The mechanism of satraplatin transport across cell membranes is through passive diffusion, predominantly as a result of its enhanced lipophilicity.
Fink et al. (Cancer Res (1996) 56, 4881) investigated the effect of the loss of DNA mismatch repair activity on the sensitivity to cisplatin, satraplatin and other platinum agents. In contrast to cisplatin and carboplatin, which form the same type of adducts in DNA, there was no difference in sensitivity between mismatch repair-proficient and mismatch repair-deficient cell lines for satraplatin.
Perego et al. (Mol Pharmacol (1998) 54, 213) investigated the sensitivity of strains of Schizosaccharomyces pombe to cisplatin, satraplatin and other platinum compounds. The panel of the 23 yeast strains tested comprised many mutants in genes that affect the response to radiation. Whereas the mutants fell into three groups with respect to their sensitivity to cisplatin (minimal change in sensitivity, hypersensitivity, and marked hypersensitivity), none of the mutants demonstrated an appreciable change in sensitivity to satraplatin.
Leyland-Jones et al. (Amer J. Pathol (1999), 155, 77) investigated genomic imbalances associated with acquired resistance to platinum analogues. Using three ovarian carcinoma cell lines they identified differences between the three platinum compounds cisplatin, satraplatin and AMD473 (picoplatin).
Amorino et al. (Int J Radiation Oncol Biol Phys (1999), 44, 399) investigated radiopotentiation by satraplatin and the role of repair inhibition. They found that satraplatin can potentiate the effects of radiation in human lung cancer cells, and that the mechanism of this effect is probably inhibition of DNA repair by satraplatin. Differences to other platinum drugs like cisplatin and carboplatin are indicated.
Vaisman et al. (Biochemistry (1999), 38, 11026) reported on the effects of DNA polymerases and high mobility group protein 1 on the carrier ligand specificity for translesion synthesis past platinum-DNA adducts, with respect to different platinum compounds.
Screnci et al. (Br J Cancer (2000) 82, 966) investigated the relationship between hydrophobicity, reactivity, accumulation and peripheral nerve toxicity of a series of platinum compounds. According to Screnci et al. the hydrophilicity of platinum drugs correlates with platinum sequestration in the peripheral nervous system, but not with neurotoxicity.
Wei et al. (J Biol Chem (2001) 276, 38774) reported on the effect of ligands on the specific recognition of intrastrand platinum-DNA cross-links by high mobility group box and TATA-binding proteins, with respect to different platinum compounds.
Fokkema et al. (Biochem Pharmacol (2002) 63, 1989) analysed in detail the satraplatin-, JM118-, and cisplatin-induced cytotoxicities in relation to various parameters like platinum-DNA adduct formation, glutathione levels and p53 status in human tumor cell lines with different sensitivities to cisplatin. It was confirmed that satraplatin and JM118 can partially circumvent intrinsic and acquired resistance to cisplatin. At equimolar basis, satraplatin induced lower levels of platinum-DNA adducts in the cell lines tested compared to cisplatin.
Taken together, fundamental differences exist between satraplatin and other platinum agents, such as cisplatin. These differences are the basis, lead to or play a role in many of the different characteristics of satraplatin, including different pharmacokinetic properties, different efficacy, a different toxicology profile, different ADME properties and different mechanisms that lead to drug resistance, only to name a few.
Receptors of the EGFR family are known targets for cancer. We show, as outlined herein, that inhibitors of receptors of the EGFR family act synergistically with certain platinum-based compounds. This synergistic effect is observed with different receptors of the EGFR family, and the synergistic effect is also not limited by the nature of the compound inhibiting the EGFR receptor. We show that antibodies, as well as small molecules, act synergistically with certain platinum-based compounds on cancer cells and tumor cells.
Pyrimidine analogues inhibit the biosynthesis of pyrimidine nucleotides and/or mimic certain metabolites of this pathway. We demonstrate that such compounds act synergistically with certain platinum-based compounds. It is asserted that this synergism is also observed between prodrugs of pyrimidine analogues or compounds that are metabolised to pyrimidine analogues in the human body.
Synergism between inhibitors of receptors of the EGFR family or chemotherapeutically active pyrimidine analogues with platinum-based chemotherapeutic agents have been demonstrated to some extent in the past. Nagourney et al (Oncology (2001) 15, 28) reported synergism between cisplatin and herceptin in breast cancer. Synergism between inhibitors of receptors of the EGFR family and cisplatin was also reported by Gieseg et al. (Anti-cancer drugs (2001) 12, 683). Mosconi et al (Eur J Cancer (1997) reported synergistic effects between gemcitabin and cisplatin.
However, as evidenced above and shown herein there are fundamental differences between the platinum-compounds of the present invention, such as satraplatin and JM-118, and other platinum compound, such as cisplatin, carboplatin and oxaliplatin. No synergistic effects have so far been reported between the platinum-compounds of the present invention and inhibitors of receptors of the EGFR family or chemotherapeutically active pyrimidine analogues.

Anti-proliferative combination therapy using certain platinum-based chemotherapeutic agents and EGFR inhibitors or pyrimidine analogues


A MEMS device having a movable mirror pixel supported on a substrate and coupled to a motion actuator so as to enable rotation of the mirror pixel about an axis lying within the mirror plane. In one embodiment, the motion actuator has a movable electrode, on which the mirror pixel is mounted. The movable electrode is supported on the substrate by a pair of upright springs, each having two parallel segments joined at one end and disjoint at the other end. One disjoint segment end is coupled to the substrate, while the other disjoint segment end is coupled to the movable electrode. The end of the upright spring corresponding to the joined segment ends points away from the substrate such that (i) the spring body protrudes through a narrow slot in the mirror pixel and (ii) the mirror plane lies at about the mid-point of the spring.

1. Field of the Invention
The present invention relates to adaptive optics and, more specifically, to micro-electromechanical systems (MEMS) for implementing adaptive optics.
2. Description of the Related Art
Adaptive optics is a field of optics dedicated to the improvement of optical signals using information about signal distortions introduced by the environment in which the optical signals propagate. An excellent introductory text on the subject is given in "Principles of Adaptive Optics" by R. K. Tyson, Academic Press, San Diego, 1991, the teachings of which are incorporated herein by reference.
A representative example of an adaptive optical element is a deformable mirror driven by a wavefront sensor and configured to compensate for atmospheric distortions that affect telescope images. Small naturally occurring variations in temperature (˜1° C.) in the atmosphere cause random turbulent motion of the air and give rise to changes in the atmospheric density and, hence, to the index of refraction. The cumulative effect of these changes along the beam propagation path may lead to beam wandering, spreading, and intensity fluctuations, each of which degrades image quality. The wavefront sensor is a device that measures the distortions introduced in the atmosphere and generates feedback for the deformable mirror. Based on the feedback, the mirror is deformed such that the beam distortions are significantly reduced, thus improving the image quality.
One frequently used type of deformable mirror is a segmented mirror, in which each segment (pixel) can individually be translated and/or rotated. For many applications, a segmented mirror is required to have: (1) for each segment, translation/rotation magnitudes on the order of 1 μm/10 degrees, respectively, and (2) for the mirror as a whole, a fill factor of at least 98%. However, for many prior-art designs, these requirements are in direct conflict with each other and therefore difficult or even impossible to meet. For example, the high fill-factor requirement suggests a solution, in which mirror support elements and motion actuators are placed beneath (hidden under) the mirror. One result of this placement is that each segment typically rotates about an axis lying below the mirror surface and therefore is subjected to a lateral displacement within the mirror plane during rotation. To prevent physical interference with the neighboring mirror segments caused by this displacement, a relatively large spacing between the segments is required. The latter, however, significantly reduces the fill factor.

MEMS device for an adaptive optics mirror


A heat exchanger for a motor vehicle air-conditioning system includes: an outer tube, and an inner tube. The outer tube has a first path inlet and a first path outlet through which a first fluid is permitted to flow. The inner tube is disposed within the outer tube and has a second path inlet and a second path outlet through which a second fluid is permitted to flow. The inner tube branches off in a first region into at least two heat exchanger tubes.

To increase the output and efficiency of motor vehicle air-conditioning systems, air-conditioning system-internal heat exchangers, so-called internal heat exchangers (IHX) are known, which thermally couple a section of the refrigerant circuit running between evaporator and compressor with a section of the refrigerant circuit running between condenser and expansion valve. In this manner the relatively cold refrigerant flowing from the evaporator to the compressor can be utilized for (pre-) cooling or sub-cooling of the comparatively warm refrigerant fed to the expansion device on the high-pressure side of the refrigerant circuit.
Thus, DE 10 2005 052 972 A1 for example describes a double-walled heat exchanger tube with an outer tube and an inner tube defining a channel between them. Here, the high-pressure refrigerant flows through the channel and the low-pressure refrigerant flows through the inner tube.
To optimize the manner of operation of such heat exchangers in the refrigerant circuit the geometrical dimensions and designs of the tubes are of overriding importance. In an existing vehicle package, which hardly offers room for the individual adaptation or changing of the outer contour or outer geometry of the heat exchanger, it is relatively difficult to individually, such as vehicle type specifically, adapt such heat exchangers with respect to their heat exchanger capacity to predetermined requirements.
Heat exchanger configurations which are known and described for example in DE 10 2005 052 972 A1 provide for example extruded or two-part section tubes with a substantially unchanged heat exchanger area in section longitudinal direction, which in this respect, dependent on the length and the diameter of the tubes, in each case can only transfer or exchange a constant amount of heat that remains the same at all times.
Compared with this, at least one object is to provide a heat exchanger with predetermined outer dimensions and outer contours which on the one hand provides an improved degree of thermal energy transfer between high-pressure side and low-pressure side of the refrigerant circuit and which on the other hand can be adapted with respect to its heat transfer or heat exchange capacity as variably and easily as possible to predetermined thermal requirements. In addition, the heat exchanger is to be characterized by low manufacturing costs and make possible a simple as well as intuitive installation. In addition, other objects, desirable features and characteristics will become apparent from the subsequent summary and detailed description, and the appended claims, taken in conjunction with the accompanying drawings and this background.

Internal heat exchanger for a motor vehicle air-conditioning system


A method of generating an embedded system (4999) from an original computer program (996) which embedded system (4999) provides a parallellized hardware (4598) and software (4599) implementation of the original computer program (996), which parallellized implementation (4598, 4599) satisfies one or more criteria regarding hardware constraints of the embedded system (4999).

Embedded systems are in widespread use, for example in consumer electronics (televisions, mobile phones, microwaves, cameras, etc.), cars, industrial robots and telecommunication systems. Embedded systems are made up of a combination of special-purpose hardware and software, designed to function optimally for the desired purpose. They differ from personal computer systems because the hardware and software is specifically designed for a limited number of functions, and the system must meet several constraints, for example on response time, power consumption, cost, size, weight or form factor.
The use of embedded systems is growing rapidly, as is their complexity. The design of embedded systems therefore is receiving increased attention, in particular with regards to performance and stability of the systems. An important aspect of embedded system design is determining which parts to implement in which processor to allow parallel execution, in which the processors are programmable RISC or DSP type processors and/or dedicated accelerators. Traditionally, this determination is almost entirely done manually, which is very time consuming. Therefore, only few partitioning options can be explored. As a result it is hard to guarantee that an optimal solution has been created that optimally satisfies the design constraints.
Partially automated techniques for creating multi-processor systems do exist but have significant constraints. One constraint in particular is that most of these techniques require the use of a domain-specific language for which the tools can easier identify opportunities for parallelism. An example is the use of CleanC to limit the programming constructs and control flow to constructs that can be statically analyzed. Similarly, design tools based on SystemC force the user to manually rewrite the functional specification into a parallel description, where the design tool only implements low-level mapping of the parallel SystemC modules to actual processors.
Such restrictions hamper the reuse of existing code. Such code has to be rewritten to conform to the limitations of the chosen language, which may not even be possible in all cases. The resulting code in addition is specific to a certain hardware platform or configuration.
What is desired is a tool that can address the problem of transforming arbitrary software source code into an improved partitioning to multiple processors.

Abstract: The system provides partitioning of functionality from the original computer program (996) using structural and behavioral program models and detects streaming and memory dependencies to improve the partitioning, relying on added indications of source lines and variables in said original computer program to relate partitions and dependencies in the program model with locations in the original program source code.


In an electronic device, a method includes analyzing help information associated with a software application to identify a sequence of manipulations of viewable elements associated with an instance of an operation by the software application. The method further includes generating a voice command set based on the sequence of manipulations of viewable elements and storing the voice command set. The method further includes receiving voice input from a user, determining the voice input represents a voice command of the voice command set, and performing an emulated manipulation sequence of viewable elements based on the voice command to actuate an instance of the operation by the software application, the emulated manipulation sequence based on the sequence of manipulations of viewable elements.

Traditionally, users have interacted with electronic devices through the manipulation of various viewable elements presented to the users, such as physical buttons or switches on a housing of an electronic device or virtual buttons and other virtual user-selectable elements presented via a display screen of an electronic device. However, to facilitate more efficient interactions, attempts have been made to implement touchless control via voice commands issued by users. A persistent impediment in achieving this goal has been the accurate translation of a voice utterance into the appropriate sequence of interactions with one or more software applications on the electronic device. One conventional approach is to provide specific application programmer interfaces (APIs) for the semantics of typical voice commands. However, due to the lack of standardization among the multitude of software applications available, this approach typically limits a user's ability to use voice commands to a very small subset of the software applications installed on an electronic device. Another conventional approach is to manually map predefined voice commands to a sequence of manipulation events. This approach suffers from similar limitations in that it is impracticable to implement on a large scale, particularly given the vast number of software applications, as well as their different versions. These problems of scale and consistency thus have prevented widespread adoption of voice control for electronic devices capable of supporting multiple software applications.

Dynamic inference of voice command for software operation from help information


To provide an epoxide-production-use catalyst that is suitably used for producing an epoxide by partial oxidation of an unsaturated hydrocarbon, a catalyst in accordance with the present invention is obtained by fixing gold fine particles to a carrier containing an oxide containing at least one of titanium and zirconium, and has an acid quantity of not more than 0.1 mmol/g determined by the NH3-TPD method. Such a catalyst for epoxide producing use can be produced by, for instance, fixing gold fine particles to a carrier having an acid quantity of not more than 0.15 mmol/g. The catalyst for epoxide producing use arranged as above is preferably used as a catalyst in partial oxidation of an unsaturated hydrocarbon to produce a corresponding epoxide.

The present invention relates to a catalyst that is suitably used for producing an epoxide by partial oxidation of an olefin compound with use of molecular oxygen in the presence of a reducing substance such as molecular hydrogen, a method for producing the foregoing catalyst for use in production of an epoxide (hereinafter referred to as epoxide-production-use catalyst), and a method for producing an epoxide by using the epoxide-production-use catalyst.
An epoxide producing method in which an olefin compound is partially oxidized with molecular oxygen in the presence of a reducing substance such as molecular hydrogen with use of a catalyst made of a titanium-containing oxide with gold fine particles fixed thereto, so as to produce an epoxide corresponding to the foregoing olefin compound, has been conventionally known (the Japanese Publications for Laid-Open Patent Applications No. 127550/1996 [Publication Date: May 21, 1996], 5590/1998 [Publication Date: Jan. 13, 1998], 244156/1998 [Publication Date: Sep. 14, 1998], and 128743/1999 [Publication Date: May 18, 1999] (Tokukaihei 8-127550, 10-5590, 10-244156, and 11-128743), and U.S. Pat. No. 5,939,569, etc.).
The foregoing catalyst exhibits a certain degree of activity at an initial stage of epoxidation, but the activity lowers as the reaction time has passed. Therefore, the catalyst presents a problem that its activity becomes insufficient when the reaction becomes in a steady state. Further, it also presents a problem that regeneration of the activity is hardly achieved even if a high-temperature heat treatment in an oxygen-containing gas for reactivation of the catalyst is applied to the catalyst whose activity has lowered.
The present invention was made in light of the foregoing problem in prior art, and an object of the present invention is to provide an epoxide-production-use catalyst that is, for instance, suitably used in partial oxidation of an unsaturated hydrocarbon to produce an epoxide corresponding to the unsaturated hydrocarbon, a method for producing the catalyst, and a method for producing an epoxide with use of the catalyst for epoxide production.
The inventors of the present invention studied the foregoing conventional catalysts, with view to solving the aforementioned problems. Consequently, they discovered that a cause of deactivation of the catalyst formed by fixing gold fine particles to a carrier containing an oxide containing at least one of titanium and zirconium is mainly related to the properties of acidic sites of the catalyst per se.
More specifically, an epoxide produced in epoxidation of an olefin is easily isomerized according to the acidic sites of the epoxide-production-use catalyst, thereby becoming an aldehyde corresponding thereto. For instance, in the case where propylene oxide is produced, propionaldehyde is produced by the foregoing isomerization. Further, in the case where the propionaldehyde resulting from the isomerization was solely brought into contact with the foregoing epoxide-production-use catalyst, an increase in the weight of the epoxide-production-use catalyst per se was observed. Further, in the case where epoxidation of propylene was carried out with use of the epoxide-production-use catalyst having been brought into contact with propionaldehyde, explicit deactivation was observed. Thus, it was found that aldehydes produced by isomerization condensed or polymerized at the acidic sites thereby becoming condensates or polymers that cover the active sites and impair the activity of the epoxide-production-use catalyst.
The inventors of the present application further made earnest study about the foregoing epoxide-production-use catalyst. As a result, among indices indicative of the properties of acidic sites, xe2x80x9cacid quantity (for detailed explanation, see the head of the xe2x80x9cDESCRIPTION OF THE EMBODIMENTSxe2x80x9d section)xe2x80x9d that is derived from a quantity of, among ammonium that has been adsorbed on the foregoing epoxide-production-use catalyst, a portion desorbed from the same is particularly significant for maintenance of catalyst activity and also regeneration of the activity.
More specifically, the epoxide-production-use catalyst in accordance with the present invention is composed of (i) a carrier containing an oxide containing at least one of titanium and zirconium, and (ii) gold fine particles fixed onto the carrier, and is arranged so as to have an acid quantity of not more than 0.1 mmol/g, the acid quantity being derived from a quantity of ammonium that, having been adsorbed on the catalyst at temperature of 50xc2x0 C., is desorbed from the catalyst as the temperature rises from 50xc2x0 C. to 400xc2x0 C.
The epoxide-production-use catalyst arranged as above enables production of an epoxide with a high yield and a high selectivity, and further, exhibits good catalyst performance, such as less deactivation. In other words, the present invention ensures that an epoxide-production-use catalyst is provided that is suitably used for partial oxidation of an unsaturated hydrocarbon with molecular oxygen in the presence of a reducing substance so as to produce an epoxide, that is superior in activity and selectivity, and that exhibits less deactivation and easy regeneration of activity.
Furthermore, a method for producing the epoxide-production-use catalyst in accordance with the present invention is a method including the step of fixing gold fine particles to a carrier, the carrier containing an oxide that contains at least one of titanium and zirconium and having an acid quantity of not more than 0.15 mmol/g, the acid quantity being derived from a quantity of ammonium that, having been adsorbed on the catalyst at temperature of 50xc2x0 C., is desorbed from the catalyst as the temperature rises from 50xc2x0 C. to 400xc2x0 C. This method makes it possible to produce the catalyst having excellent performance.
Furthermore, a method for producing an epoxide in accordance with the present invention includes the step of partial oxidation of an unsaturated hydrocarbon with molecular oxygen in the presence of a reducing substance, with use of a catalyst, the catalyst being arranged so as to include a carrier containing an oxide containing at least one of titanium and zirconium as well as gold fine particles fixed onto the carrier, and to have an acid quantity of not more than 0.1 mmol/g, the acid quantity being derived from a quantity of ammonium that, having been absorbed in the catalyst at temperature of 50xc2x0 C., is desorbed from the catalyst as the temperature rises from 50xc2x0 C. to 400xc2x0 C. This method makes it possible to produce an epoxide from an unsaturated hydrocarbon with a high yield.
For a fuller understanding of the nature and advantages of the invention, reference should be made to the ensuing detailed description.
An epoxide-production-use catalyst in accordance with the present invention (hereinafter referred to simply as xe2x80x9ccatalyst in accordance with the present inventionxe2x80x9d as required) is a catalyst that is obtained by fixing gold fine particles to a carrier containing an oxide containing at least one of titanium and zirconium, (hereinafter referred to simply as xe2x80x9cgold-fine-particles-containing catalystxe2x80x9d as required), and that catalyst has an acid quantity, described below, of not more than 0.1 mmol/g. First of all, the definition of xe2x80x9cacid quantityxe2x80x9d and a measurement method of the same in the present invention will be described below.
Measurement of the acid quantity was performed employing TPD-70 (trade name, available from BEL JAPAN INC.) as measuring apparatus, in the following manner. First of all, about 0.5 g (W g) of a sample of acid quantity measurement (hereinafter referred to as measurement object) was accurately weighed and brought into the foregoing measuring apparatus. Subsequently, the sample was held at 280xc2x0 C. for 30 minutes while helium gas was flown through the measuring apparatus at flow rate of Soml/minute, so that water adsorbed on the measurement sample was removed. Thereafter, the temperature was lowered to 50xc2x0 C., and ammonium gas was caused to adsorb on the measurement sample under conditions of 50xc2x0 C. and 200 mmHg (about 0.263 atm) for 10 minutes. Then, after the inside of the measuring apparatus was vacuumed to 10xe2x88x923 mmHg (about 1.31xc3x9710xe2x88x926 atm), the temperature inside the measuring apparatus was raised from 50xc2x0 C. to 400xc2x0 C. at a rate of 10xc2x0 C. per minute while helium gas was flown therethrough at flow rate of 50 ml/min, and a quantity of ammonium that is desorbed from the measurement object was determined by a mass spectrometer. The xe2x80x9cacid quantityxe2x80x9d in the present invention is defined as a value of the number of moles (mmol) of desorbed ammonium divided by the weight (W g) of the measurement object. Incidentally, the aforementioned method for measuring a quantity of desorbed ammonium is sometimes referred to as xe2x80x9cNH3-TPD methodxe2x80x9d.
In the case where the acid quantity of the foregoing gold-fine-particles-containing catalyst is not higher than 0.1 mmol/g (i.e., the catalyst is in accordance with the present invention), which means that catalyst activity is high in the partial oxidation of an unsaturated hydrocarbon, it is possible to produce an epoxide with a high yield and a high selectivity. Besides, good catalyst activity can be maintained for a longer time than conventionally. Furthermore, catalyst activity, once lowered, can be easily regenerated by, for instance, a heat treatment with use of an oxygen-containing gas.
On the other hand, in the case where the acid quantity of the foregoing gold-fine-particles-containing catalyst exceeds 0.1 mmol/g, deactivation of the catalyst is remarkably promoted with time. Furthermore, if the gold-fine-particles-containing catalyst, after employed for an epoxidation reaction for several hundreds of hours, is subjected to a heat treatment by raising the temperature from 100xc2x0 C. to 500xc2x0 C. in the presence of an oxygen-containing gas as an attempt to regenerate the catalyst activity, resultant regeneration of activity is remarkably insufficient.
Incidentally, the degree of deactivation of the gold-fine-particles-containing catalyst and the degree of regeneration of the activity thereof vary particularly with the acid quantity, among the properties of acidic sites, and further, it also varies with xe2x80x9cstrength of acidic sitesxe2x80x9d as well, which is another criterion of the acidic sites. More concretely, a peak temperature of the desorption of ammonium (i.e., the temperature at which an quantity per unit time of ammonium desorbed from the catalyst exhibits a peak, the ammonium having been absorbed by the catalyst at 50xc2x0 C.) by the foregoing NH3-TPD method is preferably not higher than 150xc2x0 C. When the peak temperature exceeds 150xc2x0 C., the strength of acidic sites becomes excessively great, thereby causing epoxide generated to polymerize or condense easily. Moreover, since the desorption of once polymerizing or condensing substance from the gold-fine-particles-containing catalyst is difficult, regeneration of the catalyst whose activity has lowered becomes more difficult as well.
A method for producing the catalyst in accordance with the present invention is not particularly limited, and may be a method in which gold fine particles are fixed to a carrier that contains an oxide containing at least one of titanium and zirconium and that has an acid quantity, described above, of not more than 0.15 mmol/g.
Examples of methods for preparing a carrier whose acid quantity is adjusted to the foregoing range (carrier before acid quantity adjustment is described below in detail) include, for instance, (1) a method for preparing a carrier so that at least one kind of an element should be further carried thereon, the element being selected from among the group consisting of alkaline metal elements, alkaline earth metal elements, rare earth elements, and thallium elements (hereinafter referred to as acid quantity adjustment element carrying method), (2) a method where, before a gold compound is caused to adhere to or bonded with a carrier, at least one kind of an organic compound selected from among the group consisting of alcohols, ketones, ethers, esters, and others is brought into contact with the carrier in the absence of water, in a heated environment as required, and subsequently a heat treatment at a temperature from 150xc2x0 C. to 450xc2x0 C. is applied (hereinafter referred to as contact heat-treatment method), (3) a method where a carrier is silylated with use of a silylating reagent (hereinafter referred to as silylating method), (4) a method where a carrier is processed with at least one kind of an electron donor compound (hereinafter referred to as electron donor compound employing method), and (5) a method where a carrier is processed with heat in an atmosphere at a temperature from 500xc2x0 C. to 1200xc2x0 C., or more preferably, from 750xc2x0 C. to 1000xc2x0 C. (high-temperature calcination method). By any one of the methods, the acid quantity is decreased, ensuring that a carrier with an acid quantity of not more than 0.15 mmol/g is easily prepared.
Examples of alkaline metal elements used in the foregoing acid quantity adjustment carrying method (1) includes lithium, sodium, kalium, rubidium, cesium, and francium. Examples of alkaline earth metal elements include beryllium, magnesium, calcium, strontium, barium, and radium. Examples of rare earth elements include lanthanum, cerium, and samarium. Thallium is an example of another element applicable. Among the aforementioned elements, sodium, kalium, rubidium, cesium, magnesium, calcium, strontium, and barium are more preferable. Incidentally, a content of an individual element or a sum of the same in combination is not particularly limited as long as the acid quantity of the carrier prepared with the same does not exceed 0.15 mmol/g, but it is preferably in a range of 0.001 percent by weight (wt %) to 20 wt %, more preferably in a range of 0.5 wt % to 5 wt %, and further more preferably in a range of 0.01 wt % to 2 wt %.
Incidentally, needless to say, in the case where a carrier that contains an oxide containing at least one of titanium and zirconium is formed with the foregoing oxide fixedly provided (carried) onto a support such as silica, the foregoing element may be fixed to the support before the oxide is carried thereon, or it may be carried thereon simultaneously or after the foregoing oxide is carried thereon.
In the contact heat-treatment method (2), the fashion to bring the carrier in contact with an organic compound is not particularly limited. For instance, (a) a carrier may be immersed in the foregoing organic compound in a liquid phase, (b) a carrier may be washed in the foregoing organic compound in a liquid phase, or (c) a carrier may be exposed to the organic compound in a gas phase. Furthermore, examples of alcohols used in the contact heat-treatment method include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, octyl alcohol, and ethylene glycol. Examples of ketones include acetone, methylethylketone, and methylisobutylketone. Examples of ethers include tetrahydrofuran, and diisobutylether. Examples of esters include ethyl acetate, butyl acetate, and methyl propionate.
Incidentally, in the case where the carrier and organic compound are brought into contact in a heated environment, the temperature as a heating condition is preferably higher than room temperature and not higher than 1000xc2x0 C., or more preferably in a range from 50xc2x0 C. to 300xc2x0 C. The other conditions such as a processing time, a quantity and kind of an organic compound, etc. may be set so that the acid quantity of the carrier after the contact and heat treatment should be not more than 0.15 mmol/g.
Examples of silylating reagent used in the foregoing silylating method include organic silanes, organic silylamines, and organic silazanes. The organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, chlorodimethylphenylsilane, dimethylpropylchlorosilane, dimethyloctylchlorosilane, tributhylchlorosilane, dimethoxymethylchlorosilane, methoxytrimethylsilane, dimethoxydimethylsilane, metyltrimethoxysilane, dimethoxydiphenylsilane, trimethoxyphenylsilane, ethoxytrimethylsilane, ethyltrimethoxysilane, diethoxydimethylsilane, diethoxydiethylsilane, ethyltriethoxysilane, trimethylisopropoxysilane, methoxytripropylsilane, butyltrimethoxysilane, octyltrimethoxysilane, and acetoxytrimethylsilane.
Examples of organic silylamines include dimethylaminotrimethylsilane, diethylaminotrimethylsilane, N-trimethylsilyldimethylamine, bis(dimethylamino)dimethylsilane, methylsilatrane, N-trimethylsilylimidazole, and N-trimethylsilylpyrrolidine.
Examples of organic silazanes include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, and 1,3-diphenyltetramethyldisilazane.
Examples of the other silanizers include tetramethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-cyanopropyltrichlorosilane, 2-cyanoethyltrimethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltrimethoxysilane, 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, trimethylsilyltrifluoromethane sulfonate, N,O-bistrimethylsilylacetoamide, N-trimethylsilylacetoamide, and N,Nxe2x80x2-bistrimethylsilyl urea.
Incidentally, a processing time for silylation, a quantity and kind of the silylating reagent used, etc. may be set so that the acid quantity of the resultant carrier should be not more than 0.15 mmol/g.
Examples of the electron donor compounds used in the electron donor compound employing method (4) include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds. Nitrogen-containing compounds, though not particularly limited, include: aliphatic amines such as morpholine and its derivatives, and aromatic amines such as aniline, pyridine, picoline, lutidine, quinoline, pyrrole, indole, carbazole, and derivatives of these compounds. The foregoing nitrogen-containing compounds may be any one of primary amine, secondary amine, and tertiary amine. Sulfur-containing compounds, though not particularly limited, include thiols such as phenylmercaptane, sulfides, disulfides, thiophene, benzothiophene, and derivatives of these compounds. Phosphorus-containing compounds include primary phosphines, secondary phosphines, tertiary phosphines, and phosphine oxides, though not particularly limited.
Incidentally, a processing time for processing an electron donor compound, a quantity and kind of the electron donor compound used, etc. may be set so that the acid quantity of the resultant carrier should be not more than 0.15 mmol/g.
Examples of atmospheres in the heat treatment in the foregoing high-temperature calcination method (5) include a oxygen-gas-containing atmosphere, a hydrogen-gas-containing atmosphere, and an atmosphere containing an inert gas such as argon, helium, or nitrogen. Incidentally, a processing time, etc. for high-temperature calcination may be set so that the acid quantity of the resultant carrier should be not more than 0.15 mmol/g.
These methods (1) through (5) for adjusting the acid quantity of the carrier may be used individually, or more than two selected from the same may be used in combination as required.
The xe2x80x9ccarrierxe2x80x9d used in the present invention that is processed by the foregoing acid quantity adjusting method so as to have an acid quantity of not more than 0.15 mmol/g is not particularly limited, as long as it is characterized by: (1) containing an oxide containing at least one of titanium and zirconium; (2) being capable of carrying gold fine particles; and (3) having an acid quantity exceeding 0.15 mmol/g before being processed.
The kind of the oxide containing at least one of titanium and zirconium (hereinafter referred to simply as oxide as required) is not particularly limited, but examples of oxides containing titanium (titanium-containing oxide) include, for instance, titanium oxides, titanium-containing composite oxides, and titanium-containing silicates. Among these titanium-containing oxides, those having a relatively great specific surface area are particularly preferable. Note that the shape of the titanium-containing oxide is not particularly limited, and it may be used in particulate form.
Among the foregoing titanium-containing oxides, titanium oxides having a primary particle diameter in a range of 10 nm to 200 nm and a relatively great specific surface area of not less than 5 m2/g are more preferable. Incidentally, however, the primary particle diameter and the specific surface area of titanium oxides are not particularly limited to the above-described ranges.
The foregoing titanium-containing composite oxide is not particularly limited as long as it is a composite formed with titanium that is chemically bonded with another element, such as silicon, via oxygen atoms. More specifically, it is preferably a titanium-containing composite with a relatively large specific surface area, such as titania-silica, titania-alumina, or titania-zirconia. Among these titanium-containing composite oxides, those formed with an oxide carrier that has a specific surface area of not less than 50 m2/g and that carries a titanium oxide with a high density dispersion are more preferably applicable.
The foregoing titanium-containing silicate is not particularly limited as long as it is a silicate containing titanium. A porous material containing titanium in silica matrix is particularly preferable among others, and it is more preferably applicable if it has a relatively large specific surface area and is arranged so that titanium atoms (Ti4+) is isolatedly dispersed in the silicate with a high density. Such titanium-containing silicates are known, examples of which include a material in which some of aluminum atoms composing a zeolite (X,Y type, ZSM-5, ZSM-48, etc.) material are substituted with titanium atoms so that titanium atoms are incorporated in the zeolite lattice; a material in which a part of mesoporous silica (MCM-41, MCM-48, MCM-50, etc.) having mesopores is substituted with titanium atoms; and titanosilicalite (TS-1, TS-2, etc.), which is a composite oxide of titanium and silicon and is microporous. It is also possible to use a material prepared by causing any one of these titanium-containing silicates to carry a very small quantity of titanium oxide with a high dispersion.
An atomic ratio between titanium and silicon (Ti/Si) in a titanium-containing silicate is preferably in a range of 0.1/100 to 20/100, or more preferably in a range of 1/100 to 10/100. A catalyst obtained with use of a titanium-containing silicate in which a ratio of titanium is smaller than that described above has substantially identical catalyst performance to those of a catalyst in which simple silica is used as a carrier. This is incapable of causing selective partial oxidation of olefin that is an unsaturated hydrocarbon, therefore not preferable at all.
On the other hand, examples of oxide containing zirconium (hereinafter referred to as zirconium-containing oxide as required) include zirconium oxides, zirconates, zirconium-containing composite oxides, silicates that contains zirconium and that has a porous structure (referred to as zirconium-containing silicate as required) Among these zirconium-containing oxides, those which have large specific surface areas are particularly preferable. Incidentally , the shape of zirconium-containing oxide is not particularly limited and may be used in particulate form.
Both amorphous and crystalline zirconium oxides are included in the classification of the foregoing zirconium oxides. Taking zirconium dioxide as an example, those in crystal phases such as monoclinic, rhombic, and tetragonal phases are included as crystalline oxides.
The foregoing zirconates also may be amorphous or crystalline. Examples of zirconates include zirconates of alkaline metal, alkaline earth metal, lanthanoid metal, and actinoid metal. More concretely, magnesium zirconate, and sodium zirconate may be taken as examples.
The aforementioned zirconium-containing composite oxide is not particularly limited as long as it is a composite of zirconium chemically bonded with another element, for instance, silicon , via oxygen atoms. Concretely, oxides prepared by high-dispersion of zirconium over amorphous or crystalline silica, oxides prepared by dispersing zirconium over magnesium silicate or barium silicate are taken as examples.
Examples of the aforementioned silicates that contains zirconium and that has a porous structure (zirconium-containing silicates) include amorphous and crystalline zirconosilicates. Zirconium atoms contained in zirconosilicate are often substituted with silicon atoms in silicate. Concretely, zeolite and zirconosilicates having the molecular-sieve structure are taken as examples, and with regard to pores, zirconosilicates having micropores or mesopores are taken as examples. More concretely, the examples include zirconosilicates formed by incorporating zirconium in ZSM-5, ZSM-11, zeolite beta, and MCM-41.
The xe2x80x9ccarrierxe2x80x9d in the present invention may be composed of only a single kind selected from among the aforementioned oxides that contain at least one of titanium and zirconium, or may be composed of a plurality of the same in combination. Further, to improve the activity of epoxide-production-use catalyst finally obtained, for instance, a material obtained by fixing any one of the oxides to a support molded beforehand (described below) may be employed as the carrier.
As the xe2x80x9csupportxe2x80x9d, it is possible to use a material composed of a metal oxide or a metal of various kinds that contains neither titanium nor zirconium. Examples of materials of the support include: silica (silicon dioxide), alumina, magnesia, cordierite, zirconium oxide as a metal oxide, and ceramics as composites of these oxides; and foamed substances, honeycomb carriers (support) and pellets made of various metals. Any one of the foregoing supports may be used, or two or more selected from among those may be used in combination as required.
With a view to improving the activity of the catalyst in accordance with the present invention, among the supports mentioned above, those containing at least one of alumina and silica are preferable, or those containing silica are particularly preferable. Incidentally, cases indicated by xe2x80x9ccontaining alumina or silicaxe2x80x9d include cases in which the support contains zeolite (aluminosilicate) or silica-alumina.
Furthermore, the foregoing crystalline structure, shape, and size of the foregoing support are not particularly limited, but its specific surface area is preferably not less than 50 m2/g, or more preferably not less than 100 m2/g. In the case where the specific surface area is in the foregoing range, side reaction such as successive oxidation of a reaction product is further suppressed. In other words, the reaction for producing only a target reaction product by partial oxidation of a reactant is more selectively and efficiently carried out, whereby the performance of the catalyst in accordance with the present invention is further enhanced.
The ratio of an oxide containing at least one of titanium and zirconium to a support in the case where the oxide is fixed to the support is not particularly limited, but a ratio by weight of the oxide to the support (weight of oxide:weight of support) is preferably in a range of 1:100 to 50:100.
A method for fixing the oxide to the support (causing the oxide to be fixed onto the support) is not particularly limited, but a conventional known method is applicable, such as the sol-gel method employing alcoxide, kneading, or coating in the case where any one containing silica or alumina is used as the foregoing support. Such a method enables high dispersion of the foregoing oxide over the support in an island structure.
With a view to further improving the activity of the catalyst, it is possible to cause the following element to be carried on (contained in) the support as a component element of the catalyst in accordance with the present invention: elements of the groups 5A through 7A including vanadium, molybdenum, and manganese; elements of the group 8 including iron, cobalt, and ruthenium; elements of the groups 1B through 4B including copper, zinc, aluminum, and tin; elements of the groups 5B and 6B including phosphorus and sulfur; and elements of the group 7B including chlorine. For instance, even if an acidic element such as aluminum or molybdenum is contained, it is possible to render the xe2x80x9cacid quantityxe2x80x9d of the catalyst in accordance with the present invention in the foregoing prescribed range, by applying the aforementioned processing operation for lowering the acid quantity.
By fixing gold fine particles to the foregoing carrier processed so as to have an acid quantity of not more than 0.15 mol/g (more specifically, a titanium-containing oxide and/or a zirconium-containing oxide contained in the carrier), an epoxide-production-use catalyst in accordance with the present invention is produced. The size of the gold fine particle is not particularly limited, but so-called ultra-fine particles having an average particle diameter of not more than 10 nm are preferable. Further, gold carried by the carrier is preferably at a ratio of not less than 0.001 wt % with respect to a total weight of a titanium-containing oxide and a zirconium-containing oxide contained in the carrier, more preferably in a range of 0.001 wt % to 20 wt % or further more preferably in a range of 0.02 wt % to 10 wt %. An amount of carried gold of less than 0.001 wt % is not preferable since it causes the activity of the epoxide-production-use catalyst to lower. On the other hand, an amount of carried gold of more than 20 wt % is not preferable, either, since in such a case a further improvement of the activity of the epoxide-production-use catalyst is hardly expected as compared with the case where gold is carried at a ratio in the foregoing range, and it follows that gold is wastefully used.
To cause gold fine particles to be carried on the foregoing carrier, methods applied when gold fine particles are fixed to the carrier containing an oxide that contains at least one of titanium and zirconium can be adopted without particular limitations. More specifically, the following methods are applicable: (1) a method in which a gold-containing solid substance is obtained by vapor deposition of a gold compound on a carrier, then it is calcined; and (2) a method including a step (Step A) of preparing a solution of a gold compound dissolved in an appropriate solvent, bringing the carrier into the solution, and thereafter removing the solvent from the solution, and a step (Step B) of applying a heat treatment (calcination) a gold-containing solid substance remaining after removal of the solvent, the Steps A and B being performed in the stated order. By so doing, a gold-containing composite having gold fine particles fixed on a carrier, that is, an epoxide-production-use catalyst in accordance with the present invention is produced. Incidentally, applicable as Step A are the co-precipitation method, and the deposition method, as well as common methods such as the impregnation method, the soaking method, the ion exchanging method, etc.
By the impregnation method, a carrier is dipped in a solution dissolving a gold compound homogeneously, left for a certain period of time, and subsequently a solvent is removed by evaporation, whereby a carrier having surfaces that the gold compound in the solution adheres to or is bonded with (gold-containing solid substance) is obtained. The removal of the solvent can be carried out, for example, by means of a device such as an evaporator under reduced or normal pressures, optionally while heated.
By the soaking method, a carrier is soaked in a solution dissolving a gold compound homogeneously, then, the solution is left to stand or stirred for a certain period of time, and subsequently filtered. Consequently a carrier having surfaces that the gold compound in the solution adheres to or is bonded with (gold-containing solid substance) is filtered out. The gold-containing solid substance may be washed with an appropriate solvent as required. The temperature upon either allowing the solution with the carrier therein to stand or stirring the same is determined with thermal stability of the used gold compound taken into consideration, but generally it is preferably in a range of 0xc2x0 C. to 150xc2x0 C. Further, the leaving time or the stirring time is not particularly limited, but it is preferably in a range of 1 second to 24 hours.
By the ion exchanging method, a carrier capable of ion exchanging is brought into a solution in which a gold compound is uniformly dissolved and present in an ion form, then the solution is left to stand or stirred for a certain period of time, and subsequently the solution is filtered. Consequently a carrier having a surface bonded with the gold compound in the solution (gold-containing solid substance) is filtered out. The gold-containing solid substance filtered out may be washed with an appropriate solution as required. The temperature upon either allowing the solution with the carrier therein to stand or stirring the same is determined with thermal stability of the used gold compound taken into consideration, but generally it is preferably in a range of 0xc2x0 C. to 150xc2x0 C. Further, the leaving time or the stirring time is not particularly limited, but it is preferably in a range of 1 second to 24 hours. Incidentally, water is preferably used as a solvent for dissolving the foregoing gold compound and a solvent for washing the gold-containing solid substance.
Examples of the gold compounds used in the foregoing Step A, though not particularly limited, include: chloroauric acids such as tetrachloroauric (III) acid; sodium chloroaurates such as sodium tetrachloroaurate (III); gold cyanides and kalium cyanoaurates such as gold (I) cyanide and kalium dicyanoaurate (I); diethylamine gold (III) trichloride; gold chloride ethylenediamine13 tetraacetate; (CH3)2Au(CH3COCHCOCH3); (CH3)2Au(CF3COCHCOCH3); (CH3)2Au(CF3COCHCOCF3); (C2H5)2Au (CH3COCHCOCH3); (CH3)2Au(C6H5COCHCOCF3); CH3AuP(CH3)3; AuP(CH3)3Cl; AuP(CH3)3NO3; Au(PPh3)NO3; AuCH3(PPh3); AuCl(PPh3); Au2(CH3)6; Au(CH3)6(PPh3).
The solvent used in Step A is not particularly limited as long as it can dissolves the foregoing gold compounds. Concretely, examples of the solvents include alcohols, ketones, ethers, esters, and hydrocarbons. Examples of alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, octyl alcohol, and ethylene glycol. Examples of ketones include acetone, and methylethylketone, methylisobutylketone. Examples of ethers include tetrahydrofuran, and diisobutylether. Examples of esters include ethyl acetate, butyl acetate, and methyl propyonate. Examples of hydrocarbons include hexane, toluene, and xylene.
The concentration of the gold compound in the solution is not particularly limited, but preferably in a range of 0.01 mmol/L to 100 mmol/L in the case where the foregoing impregnation method or immersion method is adopted.
In the foregoing Step B, a heat treatment (calcination) is applied to the gold-containing solid substance obtained through the foregoing Step A, and a gold compound adhering to or bonded with the carrier is fixed to the carrier as gold fine particles. As a result, an epoxide-production-use catalyst in accordance with the present invention is produced.
Conditions of the calcination with respect to the gold-containing solid substance are not particularly limited, but the temperature is preferably in a range of 50xc2x0 C. to 800xc2x0 C., while the calcination time is in a range of 1 hour to 24 hours. To completely remove the solvent from the gold-containing solid substance obtained through the foregoing Step A, the solid compound can be dried before subjected to Step B.
The method for producing epoxides in accordance with the present invention, that is, the reaction style of partial oxidation of an unsaturated hydrocarbon with use of the epoxide-production-use catalyst thus arranged as above (epoxidation reaction) is not particularly limited, and it may be of the fixed bed type, the fluid bed type, or the moving bed type. The foregoing reaction is preferably carried out in gas phase, but is possibly carried out in liquid phase as well. In the following description, a case in which the reaction is carried out in gas phase is taken as an example.
The unsaturated hydrocarbon used as row material in the foregoing producing process is not particularly limited as long as it is a chemical compound having an olefinic double bond, but it is preferably a compound having 3 to 12 carbon atoms. Examples of such unsaturated hydrocarbons include olefins such as propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, cyclohexene, 1-methyl-1-cyclopentene, and 3-methyl-1-cyclopentene. By partial oxidation of the olefinic double bond of the unsaturated hydrocarbon, an epoxide corresponding to the unsaturated hydrocarbon is produced.
The usage of the epoxide-production-use catalyst may be appropriately set depending on the amount of the gold fine particles carried thereon, the type of the unsaturated hydrocarbon, and the reaction conditions, and are not particularly limited. However, it is preferably set so that a space velocity (SV) of the unsaturated hydrocarbon upon reaction should be in a range of 100 hrxe2x88x921 xc2x7ml/gxc2x7cat. to 10,000 hrxe2x88x921xc2x7ml/gxc2x7cat. (space velocity per 1 g of catalyst).
The reducing substance, though not particularly limited, is preferably at least one kind selected from among the group consisting of hydrogen, carbon monoxide, nitrogen monoxide, dinitrogen monoxide, alcohols, aldehydes, phenols, formic acids, oxalic acids, and cyclohexadienes. Hydrogen is particularly preferable.
The usage of the reducing substance, though not particularly limited, is preferably such that a volumetric ratio of the reducing substance to the unsaturated hydrocarbon (reducing substance/unsaturated hydrocarbon) should be in a range of 1/10 to 100/1. Since the reaction velocity increases as the amount of the reducing substance increases, the volumetric ratio is preferably as approximate to 100/1 as possible. The presence of the reducing substance in the reaction system ensures that the formation of epoxide takes place even at a low temperature such as not higher than 50xc2x0 C. Incidentally, without the presence of a reducing substance in the reaction system, a reaction of the unsaturated hydrocarbon occurs at a temperature not lower than 200xc2x0 C., hardly producing an epoxide but being completely oxidized to carbon dioxide and water.
The usage of oxygen, though not particularly limited, is preferably such that a volumetric ratio between oxygen and an unsaturated hydrocarbon (oxygen/unsaturated hydrocarbon) should be in a range of 1/10 to 10/1. Usage of oxygen smaller than the foregoing range is not preferable since in such a case the yield of epoxide lowers. On the other hand, an increase in the usage of oxygen so as to exceed the foregoing range is not preferable, since with such an increase, any improvement of the yield of an epoxide cannot be expected, while the selectivity lowers.
In the epoxide producing method in accordance with the present invention, partial oxidation of an unsaturated hydrocarbon is promoted by bringing row material gas including the unsaturated hydrocarbon, a reducing substance such as hydrogen, and oxygen into contact with an epoxide-production-use catalyst in accordance with the present invention. Therefore, preferable as a reaction method is a method in which the epoxide-production-use catalyst is filled in a reaction device and the foregoing row material gas is flown through the foregoing reaction device. By the foregoing method, a gas containing a target epoxide is produced. The row material gas may be diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide as required. The usage of the inert gas is not particularly limited. Incidentally, the type of reaction is not particularly limited, but the continuous type is preferable since the foregoing reaction is a gas-phase heterogeneous catalyst reaction.
The reaction temperature may be set according to the type of the unsaturated hydrocarbon, its combination with an epoxide-production-use catalyst, etc. and is not particularly limited. However, it is preferably set so that the unsaturated hydrocarbon and the epoxide can remain in gas phase, that is, in a range of 0xc2x0 C. to 350xc2x0 C., for instance, or more preferably in a range of 20xc2x0 C. to 280xc2x0 C. An excessively low reaction temperature is not preferable since it causes the yield of the epoxide to lower. On the other hand, an excessively high reaction temperature is not preferable, either, since it causes complete oxidation of the unsaturated hydrocarbon and epoxide, thereby producing carbon dioxide and water, resulting in that the selectivity of the epoxide lowers and that a quantity of a reducing substance consumed upon combustion increases.
The reaction pressure is not particularly limited and may be set according to the reaction conditions such as the reaction temperature, but it is preferably set so that the unsaturated hydrocarbon and the epoxide can remain in gas phase, that is, in a range of 0.01 MPa to 2 MPa, for instance. An excessively low reaction pressure is not preferable since it causes the yield of the epoxide to lower. On the other hand, an excessively high reaction pressure, though causing the yield of the epoxide to increase, is not practical (industrial) since in such a case an equipment such as compressor is required. The reaction time may be set according to reaction conditions such as a reaction temperature or a reaction pressure, and is not particularly limited.
In the epoxide producing method in accordance with the present invention, direct oxidation in gas phase, that is, gas-phase oxidation reaction, requires only a single step (single stage) of the reaction process. This enables obtainment of an epoxide from an unsaturated hydrocarbon with a high yield and a high selectivity (high conversion), as well as decrease of the amount of the reducing substance thus combusted. Consequently, the amount of the reducing substance consumed can be reduced as compared with that in the case of the conventional method. In short, the present invention can provide a method whereby an epoxide is obtained from an unsaturated hydrocarbon with a high yield and a high selectivity.
Incidentally, in the case where the reaction of partial oxidation of an unsaturated hydrocarbon is carried out in liquid phase, various types of reaction including the batch type, the semi-batch type, and the continuous flow type are adoptable. The reaction temperature and pressure in the liquid-phase reaction are preferably set so that the unsaturated hydrocarbon and the epoxide can remain in gas phase, that is, not higher than 150xc2x0 C. with regard to the temperature and in a range of 0.05 MPa to 10 MPa with regard to the pressure.
Alternatively, an inert solvent with respect to the reaction may be used so that the foregoing reaction should be carried out in liquid phase. Applicable as a reaction method using a solvent is a method in which the aforementioned row material gas is bubbled in a suspension obtained by suspending the epoxide-production-use catalyst in accordance with the present invention in a solvent. Examples of the foregoing solvents include aromatic hydrocarbons such as benzene, etc., and halogenized hydrocarbons such as methylene chloride, etc., though not particularly limited. The usage of the solvent is not particularly limited.
The following description will explain the present invention in more detail, with examples and comparative examples. The present invention, however, is not limited by the following description at all.

Catalyst for use in production of epoxide, method for producing the catalyst, and method for producing epoxide


Reference markers are attached to rails and/or other dynamically moving components of railroad tracks, and/or located at fixed and stationary positions adjacent to the track. When images of railway rolling stock are obtained, the reference marker(s) appear in the image. Accordingly, measurements of various aspects and parameters of various components of the railway rolling stock can be obtained at high precision and/or accuracy relative to the railroad track component to which the reference marker is attached and/or relative to the stationary position. The reference markers allow one or more images, obtained at some intervening time interval, to be accurately and precisely aligned relative to the reference marker(s) regardless of the dynamic motion of the railroad track component(s) and/or of the rolling stock that occurred as the images were captured. The reference markers can include optical, thermal or other indicia. The indicia have known dimensions and/or known distances from an image capture device.

1. Field of the Invention
This invention is directed to obtaining higher accuracy measurements of the rolling stock of a railroad.
2. Related Art
The rolling stock of a railroad, such as box cars, flat cars, tanker cars, hopper cars, gondolas, piggy back carriers for semi-tractor trailers and/or containers, passenger cars, and the like, are subject to wear, fatigue and the like. This is especially true of the wheels and trucks of such rolling stock. Accordingly, it is typically necessary or desirable to inspect such rolling stock, and especially the trucks and wheels of such rolling stock, on occasion to insure that the rolling stock remains safe to use and is not likely to experience a breakdown in the interval between the current inspection and the next inspection of that piece of rolling stock.
Traditionally, such inspections were performed manually. Not only was such manual inspection time consuming and expensive, it was difficult to insure that a given piece of rolling stock was inspected on any reasonable schedule.
Accordingly, as set forth in U.S. Pat. Nos. 6,911,914; 6,909,514; 6,872,945; 6,823,242; 6,768,551; 5,793,492; 5,677,533; 5,596,203; 5,448,072; 5,247,338; 3,253,140; and 3,206,596, each of which is incorporated herein by reference for its teachings, over the last thirty years, various systems and methods have been developed for automatically inspecting various aspects and parameters of railway rolling stock, such as railroad wheel and bearing temperatures, hot rail car surfaces, wheel profiles, and the like. Conventionally, such systems and methods have used passive sensors that generate a 1-dimensional, time-varying signal as the piece of rolling stock passes by the sensor. To provide additional dimensional information, multiple sensors can be arranged either along or perpendicular to the railway rail. More recently, optical-based systems that generate 2-dimensional images of various components of railway rolling stock, such as wheels, truck assemblies, car bodies of the rolling stock and the like, have been used to inspect such rolling stock.

Systems and methods for obtaining improved accuracy measurements of moving rolling stock components


An interface card module applied in a computer system is provided. The interface card module includes an interface card and an adapter. The interface card includes at least one interface card connector disposed on a first side of the interface card. The first side is fastened on a case of the computer system. The adapter is electrically connected to the interface card connector. The adapter provides a first power for driving the interface card and providing partial or entire power consumed by the interface card.

1. Field of the Invention
The invention relates in general to an interface card module, and more particularly to an interface card module of a computer system.
2. Description of the Related Art
With the continual updating of computer add-on-cards such as display cards, sound cards, and network interface cards are upgraded to provide the consumers with interface cards having more versatile and more powerful functions and faster computing speed, so that the consumers can enjoy faster and more wonderful audio and visual experience with the computer. The connection between an interface card and its peripheral power device are disclosed below.
Referring to FIG. 1, a block diagram of an interface card and its power device is shown. The computer system 100 includes a motherboard 101, an interface card 103 and a power supply 105. The motherboard 101 has an interface card slot 102 disposed thereon. The interface card 103 is inserted into the interface card slot 102 through which the power is transmitted to the interface card 103 for processing operations. The interface card slot 102 may be provided with different kinds of the interface specification such as the PCI interface specification, the PCI-EXPRESS interface specification and the AGP interface specification. The interface card slot 102 of various interface specifications can provide differs power. For example, the PCI interface, the AGP interface and the PCI-EXPRESS can provide 56 Watts, 42 Watts and 75 Watts of the maximum power, respectively. Presuming the user needs to insert a new model interface card 103, which requires 150 Watts, but the PCI-EXPRESS interface card slot 102 can provide 75 Watts only. In other words, in order to drive the new model interface card 103, another 75 Watts are required. The current practice to resolve the above problem is connecting the power supply 105 to the interface card 103 for providing the additional 75 Watts. The dotted line in FIG. 1 illustrates the power line connecting the power supply 105 to the interface card 103.
However, the interface cards are continually upgraded. Particularly, the large-scaled display devices may need to have higher resolution or the display cards may need to have faster operating speed as required by computer games, therefore a single display card or multiple display cards may be disposed on the motherboard to provide more power functions and faster operating speed. Thus, the power consumed by the interface card and various circuit components of the motherboard may exceed the maximum load of the power supply. The user needs to exchange a power supply capable of providing sufficient power.
In terms of the user, whenever an interface card is replaced or augmented, the power supply needs to be replaced at the same time. It is indeed very troublesome to replace the power supply and reset the circuits of other electronic devices, and the associated cost would increase significantly. Not only will the consumers have to tackle the extra troubles, but the disposal of the usable existing power supply is actually a waste of resources.

Computer system and interface card module thereof


A connection assembly including a first connector comprising a post, and a second connector.

To satisfy the constraints indicated above, connection assemblies of known types include a first connector and a second connector, which are fastened to one another in the fastening position by means of screws. The screws ensure reliable and proven fastening; however, the connection and disconnection operations are long, a tightening operation and a predetermined torque being necessary, and can be difficult if only a little space for screwing and unscrewing of the screws is available.
A known alternative proposed by U.S. Pat. No. 8,449,314 consists of connection assemblies the connectors of which are attached to one another in the fastening position by means of fastening hooks. These hooks are fastened to the second connector by means of counterbores machined in its sides. This fastening mode has satisfactory reliability; however, the use of hooks can cause problems if the space available for the connection and disconnection operations is very small.
Thus there exists a need for connection assemblies able to ensure a reliable connection, but the connectors of which can be connected and disconnected in a simple and rapid manner, and in a very small volume.

Connection assembly with rapid and secure fastening

Abstract: A body of the second connector comprises a fastening passage. The post can penetrate into said fastening passage by moving in a fastening direction, so as to reach a fastening position. In the fastening position, the post cannot move in a disassembly direction opposite to the fastening direction. The connectors are configured in such a manner that an external action applied solely to the post allows the post to pass from the fastening position to a free position, in which the post can move in translation in the disassembly direction.

Abstract: In fastening position, the post is in a predetermined angular range. The connection assembly further comprises angular returning means to return the post into said predetermined angular range relative to the axis of the post, when the post is fastened to a body of the first connector.


A low band width passive vehicle suspension system for utilization with land vehicles which includes a shock absorber of the cylinder-piston type suspended between each wheel of the vehicle and its chassis. The piston divides the cylinder into a pair of chambers and the chambers are interconnected with a bypass passageway within which there is mounted a variable orifice controlled by a moveable valve. Sensors are mounted on each wheel to detect movement thereof as well as acceleration roll and pitch sensors being mounted on the vehicle. Fluidic signals are developed by each of the sensors and are applied through a fluidic circuit for application to the valve structure controlling the variable orifice. By control of the orifice, the characteristics thereof are changed to in turn change the damping characteristics of each of the shock absorbing units to thereby stabilize the vehicle.

1. Field of the Invention
This invention relates to a vehicle suspension system and more particularly to a passive vehicle suspension system which includes a shock absorber having a fluid cylinder and in which the suspension properties of the fluid cylinder change in response to wheel acceleration, pitch, roll, or other movements of the vehicle.
2. Description of the Prior Art
A typical suspension system for vehicles utilize a suspension coil and a shock absorber interposed between a vehicle body and the vehicle wheel. The suspension coil spring generally resists loads applied to maintain the vehicle body and the road wheel in a predetermined positional relationship to each other. The shock absorber is typically intended to damp or absorb vibrations transmitted between the vehicle body and the road wheel. In some instances, the suspension system may be further provided with a roll-stabilizer for suppressing vehicular rolling motion.
In the recent past, it has become popular to utilize actively controlled suspension systems to provide smoother rides and more positive handling stability for vehicles, particularly automotive vehicles. Such actively controlled suspension systems may include hydraulic circuits which sense vehicle and wheel movements and in response thereto, control the application of hydraulic fluid under pressure from a source thereof through a pressure control valve to the suspension system. The control is effected by introducing or draining the pressurized working fluid with respect to a working chamber or chambers in a portion of the suspension system. Such a control unit actively performs anti-pitching, anti-rolling, suppression of wheel bouncing and the like. Although typically such prior art control suspension systems utilize hydraulic fluid, in some instances, pressurized pneumatic fluid has also been used.
Irrespective of the fluid medium utilized when an active control suspension system is utilized, such systems contain a large number of moveable parts and typically include a pump which is driven by the vehicle engine so as to maintain the source of fluid under pressure thus degrading fuel economy and adding substantially to the cost of the vehicle. Typical of such prior art active control suspension systems for vehicles are those shown in issued U.S. Pat. Nos. 4,625,994, 4,801,155, 4,911,469, and 4,982,979.


A multi-layered cladding material including a ceramic matrix composite and a metallic material, and a tube formed from the cladding material. The metallic material forms an inner liner of the tube and enables hermetic sealing of thereof. The metallic material at ends of the tube may be exposed and have an increased thickness enabling end cap welding. The metallic material may, optionally, be formed to infiltrate voids in the ceramic matrix composite, the ceramic matrix composite encapsulated by the metallic material. The ceramic matrix composite includes a fiber reinforcement and provides increased mechanical strength, stiffness, thermal shock resistance and high temperature load capacity to the metallic material of the inner liner. The tube may be used as a containment vessel for nuclear fuel used in a nuclear power plant or other reactor. Methods for forming the tube comprising the ceramic matrix composite and the metallic material are also disclosed.

Nuclear reactor fuel designs, such as pressurized water reactor and boiling water reactor fuel designs, impose significantly increased demands nuclear fuel cladding tubes. Such components are conventionally fabricated from the zirconium-based metal alloys, such as zircaloy-2 and zircaloy-4. Increased demands on such components are in the form of longer required residence times, thinner structural members and increased power output per area, which cause corrosion. Resistance to radiation damage, such as dimensional change and metal embrittlement, is one of the most important considerations in selecting cladding materials for a fuel cladding tube. Zirconium alloys are currently used as the primary cladding material for nuclear fuel in nuclear power plants because of their low capture cross-section for thermal neutrons and good mechanical and corrosion resistance properties, high thermal conductivity and high melting point.
While zirconium and other metal alloys have excellent corrosion resistance and mechanical strength in a nuclear reactor environment under normal and accident conditions where the heat fluxes are relatively low, they encounter mechanical stability problems during conditions such as a departure from nucleate boiling ("DNB") incident that might occur during accidental conditions. Any action tending to increase the heat flux of the core in order to raise the plant output will aggravate these problems. A significant in-reactor life limiting use with currently available fuel cladding tubes formed from zirconium-based alloys is corrosion, especially in the presence of water and increased operating temperatures of newer generations of nuclear reactors, such as light water reactors (LWRs) and supercritical water cooled reactors (SCWRs). For example, buildup of oxide material on the fuel cladding tubes caused by oxidation of zirconium during reactor operation may lead to adverse effects on thermal conduction. Hydrogen generated by oxidation of the zirconium in the fuel cladding tubes causes embrittlement of the zirconium and formation of precipitates in the fuel cladding tube which is under an internal gas pressure. The presence of the precipitates may reduce mechanical strength of the fuel cladding tube causing cracks in walls and end caps.
Fuel cladding tubes formed from zirconium and zirconium alloys are also susceptible to stress corrosion cracking during operation due to joint action of fission precuts and mechanical stress resulting from radiation-induced swelling of fuels. The interaction between the fuel and the cladding results in nucleation and propagation of cracks and depressurization of the fuel cladding tube. Such cracks propagate from an internal surface of the fuel cladding tube to an external surface and, thus, may rupture the cladding wall. Depressurization of the fuel cladding tube due to stress corrosion cracking significantly reduces the life of the fuel cladding tube and, in addition, reduces the output and safety of the nuclear reactor. Moreover, the fuel cladding tube may be circumferentially loaded in tension due to expansion of the contents, such as fuel pellets, within the fuel cladding tube. Deformation of the fuel cladding tube resulting from such tension increases susceptibility of the fuel cladding tube to stress corrosion failure.
Silicon carbide has also been used to form fuel cladding tubes for use in nuclear reactors. The silicon carbide fuel cladding tubes are porous structures that are difficult to achieve reliable hermetic sealed around the nuclear fuel. Thus, ceramic material debris dislodged from the silicon carbide fuel cladding tubes during use may reside between the fuel and the ceramic cladding and may be a source of local stress concentration during normal fuel swelling. The release of such ceramic material debris causes localized thermal and mechanical damage in the silicon carbide fuel cladding tubes, eventually causing failure thereof.
Given the resurgence of nuclear energy development worldwide there is a significant need today for both safety and economical performance enhancements to power plant or other reactor operations. Improved fuel cladding tubes that reduce operation costs and increase safety during reactor accidents are desirable.

Cladding material, tube including such cladding material and methods of forming the same


A deployable device includes a supporting structure, a mandrel able to move in rotation with respect to the supporting structure about a first axis Z, a membrane able to pass from a rolled-up configuration rolled up around the mandrel about the first axis Z to a deployed configuration deployed along a second axis X substantially perpendicular to the first axis Z. The device comprises two fittings secured to the mandrel at their centre, arranged one on either side of the membrane and comprising first stubs on their periphery, a casing extending between the two fittings, the casing comprising second stubs of a shape complementing the shape of the first stubs, the casing being able to pass from a rolled-up configuration at least partially enveloping the membrane in the rolled-up configuration to a deployed configuration at least partially superposed on the membrane in the deployed configuration.

In the field of space, tape springs are often used in deployment. In the stored (or rolled-up) position, tape springs are rolled up around a mandrel. Deployment of tape springs occurs autonomously as they spontaneously unroll when the mandrel is free to rotate. Spring tapes are known in the field of space as being flexible tapes having a cross section in the form of an arc of a circle of which the radius of curvature is convex on a first face and concave on a second face, these tapes being able to pass from the rolled-up state to the deployed state essentially by virtue of their own elastic energy. There are various types of tape that each have their own properties. Monostable tapes have a deployed natural position and require retention to hold them in the stored position. Monostable tape springs therefore have a natural tendency to deploy in order to return to their unrolled state. The deployment of monostable tapes is often haphazard and uncontrolled. Bistable tapes have two natural positions (rolled-up position and deployed position). Their deployment is linear and controlled.
Where there is a wish to deploy a structure using tape springs, it is necessary for the tape springs to hold the object in the rolled-up configuration and maintain the rigidity of the assembly during deployment. The mandrel may be connected to the bearing structure at its ends. That makes it possible to optimize the useful surface area, for example of the membrane rolled up around the mandrel and on which solar cells are arranged. It also makes it possible to minimize interfaces for catching on the bearing structure. This type of configuration meets the requirements associated with deployable devices, which are connected with the problems of compactness and rigidity in the stored configuration and optimization of onboard mass.
In the configuration known from the prior art, in which configuration the mandrel is connected to the bearing structure at its ends, the mandrel has to be able to react all the loads of launch. Because its diameter is limited by the constraint of available storage volume, the load-reacting capabilities of the mandrel are also limited.
This becomes particularly problematical in the case of large deployable structures which require greater launch loads.
In order to address this problem, existing solutions are based on the addition of stowage on the central part of the mandrel. For example, a stowage band is connected to the mandrel to contribute to reacting the loads. Depending on the size of the deployable structure, there may also be two or three stowage bands. This results in a reduction in the useful surface area. Furthermore, the addition of additional stowage has an impact on the performance of the structure in terms of the onboard mass and the frequency in the deployed configuration. Finally, additional stowage may also present a risk of nondeployment of the structure.

Deployable tape spring device having a rollable membrane and casing, and satellite including the same


Methods, systems, and computer readable media for facilitating trading two items (L,Q) from the group of items comprising commodities and financial instruments. At least two agents (2) want to trade the items (L,Q). There is a trading channel (3) between the two agents (2) allowing for the execution of trades. There are flow (trading) limits on the items being traded. A central computer (1) is coupled to the two agents (2). Said computer (1) is adapted to convey to each agent (2) current tradable bid and offered prices and sizes subject to the agent's (2) trading limits.

Wright, Ben, "Unlocking the C2C forex riddle", euromoney.com, Jul. 25, 2001, U.K., provides a general discussion of some of the business aspects of the present invention.
Morris, Jennifer, "Forex goes into future shock", Euromoney, October 2001, gives a general description of several computerized foreign exchange platforms, including one described in the present patent application.
Ahuja, R. K., Magnanti, T. L., and Orlin, J. B., Network Flows; Theory, Algorithms, and Applications, Chapters 7 and 9 (Prentice-Hall, Inc. 1993), U.S.A., sets forth some algorithms that may be useful in implementing the present invention.
U.S. Pat. No. 5,375,055 discloses a relatively simple trading system that is capable of implementing only single-hop trades. On the other hand, the present invention can accommodate multi-hop trades. Further, in U.S. Pat. No. 5,375,055, the user is given information that suggests to him that he can take a trade when he may not have enough credit to take the whole trade. In the present invention, on the other hand, if only part of a trade can be executed, that information is given to the user; the user knows that he has enough credit to execute at least the best bid and best offer that are displayed on his computer.
An even simpler trading system is disclosed in European patent application 0 411 748 A2 and in granted European patents 0 399 850 B1 and 0 407 026 B1, all three of which are assigned to Reuters Limited. These Reuters documents describe a system in which information concerning a potential trade is displayed even if the user can't execute it at all. In the present invention, such a potential trade would not be displayed at all. Furthermore, the only credit limits that can be accommodated in the Reuters system are volume limits for the purposes of limiting settlement risk. In the present invention, any agent may set credit limits in multiple ways so as to limit not only settlement risk (measured both by individual instrument volumes and by notional absolute values) but also exposure risk. Furthermore, the Reuters keystations require a human operator. In the present invention, on the other hand, an API (application programming interface) enables any participant to develop programs which partially or fully automate the trading process.

Valaquenta Intellectual Properties Limited