Novel Aerosol-Generating Substrate Comprising Illicium Species

This application is a continuation of and claims benefit under 35 U.S.C. § 120 to U.S. patent application Ser. No. 17/769,850, filed Apr. 18, 2022, which is a U.S. national stage application of PCT/EP2020/079364, filed Oct. 19, 2020, and claims the benefit of priority under 35 U.S.C. § 119 from EP19204406.3, filed Oct. 21, 2019, the entire contents of each of which are incorporated herein by reference.

The present invention relates to aerosol-generating substrates comprising homogenised plant material formed from star anise particles and to aerosol-generating articles incorporating such an aerosol-generating substrate. The present invention further relates to an aerosol derived from an aerosol-generating substrate comprising star anise particles.

Aerosol-generating articles in which an aerosol-generating substrate, such as a tobacco-containing substrate, is heated rather than combusted, are known in the art. Typically in such articles, an aerosol is generated by the transfer of heat from a heat source to a physically separate aerosol-generating substrate or material, which may be located in contact with, within, around, or downstream of the heat source. During use of the aerosol-generating article, volatile compounds are released from the substrate by heat transfer from the heat source and are entrained in air drawn through the article. As the released compounds cool, they condense to form an aerosol.

Some aerosol-generating articles comprise a flavourant that is delivered to the consumer during use of the article to provide a different sensory experience to the consumer, for example to enhance the flavour of aerosol. A flavourant can be used to deliver a gustatory sensation (taste), an olfactory sensation (smell), or both a gustatory and an olfactory sensation to the user inhaling the aerosol. It is known to provide heated aerosol-generating articles that include flavourants.

It is also known to provide flavourants in conventional combustible cigarettes, which are smoked by lighting the end of the cigarette opposite the mouthpiece so that the tobacco rod combusts, generating inhalable smoke. One or more flavourants are typically mixed with the tobacco in the tobacco rod in order to provide additional flavour to the mainstream smoke as the tobacco is combusted. Such flavourants can be provided, for example, as essential oil.

Aerosol from a conventional cigarette, which contains a multitude of components interacting with receptors located in the mouth provides a sensation of “mouthfullness,” that is to say, a relatively high mouthfeel. “Mouthfeel,” as used herein refers to the physical sensations in the mouth caused by food, drink, or aerosol, and is distinct from taste. It is a fundamental sensory attribute which, along with taste and smell, determines the overall flavour of a food item or aerosol.

There are difficulties involved in replicating the consumer experience provided by conventional combustible cigarettes with aerosol-generating articles in which the aerosol-generating substrate is heated rather than combusted. This is partially due to the lower temperatures reached during the heating of such aerosol-generating articles, leading to a different profile of volatile compounds being released.

It would be desirable to provide a novel aerosol-generating substrate for a heated aerosol-generating article providing an aerosol with improved flavour and mouthfullness. It would be particularly desirable if such an aerosol-generating substrate could provide an aerosol with a sensorial experience that is comparable to that provided by a conventional combustible cigarette. It would also be particularly desirable if such an aerosol-generating substrate could provide an aerosol that has reduced levels of undesirable aerosol compounds compared to existing aerosol-generating substrates, for example those containing tobacco only.

It would further be desirable to provide such an aerosol-generating substrate that can be readily incorporated into an aerosol-generating article and which can be manufactured using existing high-speed methods and apparatus.

The present disclosure relates to an aerosol-generating article comprising an aerosol-generating substrate, the aerosol-generating substrate formed of a homogenised plant material including star anise particles, referred to as a “homogenised star anise material”. The homogenised star anise material may further comprise an aerosol former. The homogenised star anise material may further comprise a binder. The aerosol-generating substrate may comprise at least about 70 micrograms of (E)-anethole per gram of the substrate, on a dry weight basis. The aerosol-generating substrate may comprise at least about 50 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis. The aerosol-generating substrate may comprise at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

According to the invention there is provided an aerosol-generating article comprising an aerosol-generating substrate, the aerosol-generating substrate comprising a homogenised plant material including star anise particles. According to the invention, the aerosol-generating substrate comprises: at least about 70 micrograms of (E)-anethole per gram of the substrate, on a dry weight basis; at least about 50 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis; and at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

According to the invention there is provided an aerosol-generating article comprising an aerosol-generating substrate, the aerosol-generating substrate formed of a homogenised star anise material including star anise particles. According to the invention, the homogenised star anise material comprises: star anise particles, an aerosol former and a binder. The aerosol-generating substrate comprises: at least about 70 micrograms of (E)-anethole per gram of the substrate, on a dry weight basis; at least about 50 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis; and at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

Preferably, upon heating of the aerosol-generating substrate of the aerosol-generating article according to the present invention according to Test Method A as described below, an aerosol is generated comprising: at least about 20 micrograms of (E)-anethole per gram of the substrate, on a dry weight basis; at least about 10 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis; and at least about 3.5 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis. According to the invention, the amount of (E)-anethole per gram of the substrate is no more than about 5 times the amount of epoxyanethole per gram of the substrate and the amount of (E)-anethole per gram of the substrate is no more than about 10 times the amount of benzyl isoeugenol ether per gram of the substrate.

Preferably, upon heating of the aerosol-generating substrate according to Test Method A, the aerosol generated from the aerosol-generating substrate comprises: (E)-anethole in an amount of at least about 0.4 micrograms per puff of aerosol; epoxyanethole in an amount of at least about 0.2 micrograms per puff of aerosol; and benzyl isoeugenol ether in an amount of at least about 0.1 micrograms per puff of aerosol, wherein a puff of aerosol has a volume of 55 millilitres as generated by a smoking machine. According to the invention, the amount of (E)-anethole per puff is no more than about 5 times the amount of epoxyanethole per puff and the amount of (E)-anethole per gram of the homogenised plant material is no more than about 10 times the amount of benzyl isoeugenol ether per puff.

The present disclosure also relates to an aerosol-generating substrate formed of a homogenised plant material comprising star anise particles, referred to herein as “homogenised star anise material”. The homogenised star anise material may further comprise an aerosol former. The homogenised star anise material may further comprise a binder. The aerosol-generating substrate may comprise at least about 70 micrograms of (E)-anethole per gram of the substrate, on a dry weight basis; at least about 50 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis; and at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

According to the invention there is also provided an aerosol-generating substrate formed of a homogenised star anise material, wherein the homogenised star anise material comprises star anise particles, an aerosol former and a binder. The aerosol-generating substrate comprises at least about 70 micrograms of (E) anethole per gram of the substrate, on a dry weight basis; at least about 50 micrograms of epoxyanethole per gram of the substrate, on a dry weight basis; and at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

The present invention further provides an aerosol produced upon heating of an aerosol-generating substrate, the aerosol comprising: (E)-anethole in an amount of at least about 0.4 micrograms per puff of aerosol; epoxyanethole in an amount of at least about 0.2 micrograms per puff of aerosol; and benzyl isoeugenol ether in an amount of at least about 0.1 micrograms per puff of aerosol, wherein a puff of aerosol has a volume of 55 millilitres as generated by a smoking machine of Test Method A. According to the invention, the amount of (E)-anethole per puff is no more than about 5 times the amount of epoxyanethole per puff and the amount of (E)-anethole per gram of the homogenised plant material is no more than about 10 times the amount of benzyl isoeugenol ether per puff.

The present invention further provides a method of making an aerosol-generating substrate comprising: forming a slurry comprising star anise particles, water, an aerosol former, a binder and optionally tobacco particles; casting or extruding the slurry in the form of a sheet or strands; and drying the sheets or strands, preferably at a temperature of between 80 and 160 degrees Celsius. Where a sheet of aerosol-generating substrate is formed, the sheet may optionally be cut into strands or gathered the sheet to form a rod. The sheet may optionally be crimped prior to the gathering step.

Any references below to the aerosol-generating substrates and aerosols of the present invention should be considered to be applicable to all aspects of the invention, unless stated otherwise.

As used herein, the term “aerosol-generating article” refers to an article for producing an aerosol, wherein the article comprises an aerosol-generating substrate that is suitable and intended to be heated or combusted in order to release volatile compounds that can form an aerosol. A conventional cigarette is lit when a user applies a flame to one end of the cigarette and draws air through the other end. The localised heat provided by the flame and the oxygen in the air drawn through the cigarette causes the end of the cigarette to ignite, and the resulting combustion generates an inhalable smoke. By contrast, in “heated aerosol-generating articles”, an aerosol is generated by heating an aerosol-generating substrate and not by combusting the aerosol-generating substrate. Known heated aerosol-generating articles include, for example, electrically heated aerosol-generating articles and aerosol-generating articles in which an aerosol is generated by the transfer of heat from a combustible fuel element or heat source to a physically separate aerosol-generating substrate.

Also known are aerosol-generating articles that are adapted to be used in an aerosol-generating system that supplies the aerosol former to the aerosol-generating articles. In such a system, the aerosol-generating substrate in the aerosol-generating articles contain substantially less aerosol former relative to those aerosol-generating substrate which carries and provides substantially all the aerosol former used in forming the aerosol during operation.

As used herein, the term “aerosol-generating substrate” refers to a substrate capable of producing upon heating volatile compounds, which can form an aerosol. The aerosol generated from aerosol-generating substrates may be visible to the human eye or invisible and may include vapours (for example, fine particles of substances, which are in a gaseous state, that are ordinarily liquid or solid at room temperature) as well as gases and liquid droplets of condensed vapours.

As used herein, the term “homogenised plant material” encompasses any plant material formed by the agglomeration of particles of plant. For example, sheets or webs of homogenised plant material for the aerosol-generating substrates of the present invention may be formed by agglomerating particles of plant material obtained by pulverising, grinding or comminuting star anise plant material and optionally tobacco material such as tobacco leaf lamina or tobacco leaf stems. The homogenised plant material may be produced by casting, extrusion, paper making processes or other any other suitable processes known in the art.

As used herein, the term “homogenised star anise material” refers to a homogenised plant material comprising star anise particles, optionally in combination with tobacco particles. The term “homogenised tobacco material” refers to a homogenised plant material comprising tobacco particles but no star anise particles, which is therefore not in accordance with the invention.

As used herein, the term “star anise particles” encompasses particles derived from the dried fruits of plants of the genuspreferably particles derived fromHooker fil. (Illiciaceae).

By contrast, star anise essential oil is a distillate and (E)-anethole is a compound derived from star anise. These are not considered star anise particles and are not included in the percentages of particulate plant material.

The present invention provides an aerosol-generating article incorporating an aerosol-generating substrate formed of a homogenised plant material including star anise particles, referred to herein as “homogenised star anise material”. The present invention also provides an aerosol derived from such an aerosol-generating substrate. The inventors of the present invention have found that through the incorporation of star anise particles into the aerosol-generating substrate, it is advantageously possible to produce an aerosol which provides a novel sensory experience. Such an aerosol provides unique flavours and may provide an increased level of mouthfullness.

In addition, the inventors have found that it is advantageously possible to produce an aerosol with an improved star anise aroma and flavour compared to the aerosol produced through the addition of star anise additives such as star anise oil. Star anise oil is distilled from the leaves, fruits and seeds of the star anise tree and has a composition of flavourants that are different from star anise particles, presumably due to the distillation process which may selectively remove or retain certain flavourants. Moreover, in certain aerosol-generating substrates provided herein, star anise particles may be incorporated at a sufficient level to provide the desired star anise flavour whilst maintaining sufficient tobacco material to provide the desired level of nicotine to the consumer.

Furthermore, it has been surprisingly found that the inclusion of star anise particles in an aerosol-generating substrate provides a significant reduction in certain undesirable aerosol compounds compared to an aerosol produced from an aerosol-generating substrate comprising 100 percent tobacco particles without star anise particles.

The flavour released by star anise is due to the presence of one or more volatile flavourants which are volatilised and transferred to the aerosol upon heating. (E)-anethole (E)-1-methoxy-4-(1-propeny)benzene, chemical formula: CHO, Chemical Abstracts Service Registry Number 25679-28-1) typically makes up between about 80% and about 90% of star anise essential oil (Chemical Abstracts Service Registry Number 8007-70-3) by mass.

The presence of star anise in homogenised plant material (such as cast leaf) can be positively identified by DNA barcoding. Methods for performing DNA barcoding based on the nuclear gene ITS2, the rbcL and matK system as well as the plastid intergenic spacer trnH-psbA, are well known in the art and can be used (Chen S, Yao H, Han J, Liu C, Song J, et al. (2010) Validation of the ITS2 Region as a Novel DNA Barcode for Identifying Medicinal Plant Species. PLoSONE 5(1): e8613; Hollingsworth P M, Graham S W, Little D P (2011) Choosing and Using a Plant DNA Barcode. PLoS ONE 6(5): e19254).

The inventors have carried out a complex analysis and characterisation of the aerosols generated from aerosol-generating substrates of the present invention incorporating star anise particles and a mixture of star anise and tobacco particles, and a comparison of these aerosols with those produced from existing aerosol-generating substrates formed from tobacco material without star anise particles. Based on this, the inventors have been able to identify a group of “characteristic compounds” that are compounds present in the aerosols and which have derived from the star anise particles. The detection of these characteristic compounds within an aerosol within a specific range of weight proportion can therefore be used to identify aerosols that have derived from an aerosol-generating substrate including star anise particles. These characteristic compounds are notably not present in an aerosol generated from tobacco material. Furthermore, the proportion of the characteristic compounds within the aerosol and the ratio of the characteristic compounds to each other are clearly indicative of the use of star anise plant material and not a star anise oil. Similarly, the presence of these characteristic compounds in specific proportions within an aerosol-generating substrate is indicative of the inclusion of star anise particles in the substrate.

In particular, the defined levels of the characteristic compounds within the substrate and the aerosol are specific to the star anise particles present within the homogenised star anise material. The level of each characteristic compound is dependent upon the way in which the star anise particles have been processed during production of the homogenised star anise material. The level is also dependent upon the composition of the homogenised star anise material and in particular, will be affected by the level of other components within the homogenised star anise material. The level of the characteristic compounds within the homogenised star anise material will be different to the level of the same compound within the starting star anise material. It will also be different to the level of the characteristic compounds within materials containing star anise particles but that are not in accordance with the invention as defined herein.

In order to carry out the characterisation of the aerosols, the inventors have made use of complementary non-targeted differential screening (NTDS) using liquid chromatography coupled to high-resolution accurate-mass mass spectrometry (LC-HRAM-MS) in parallel with two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS).

Non-targeted screening (NTS) is a key methodology for characterising the chemical composition of complex matrices by either matching unknown detected compound features against spectral databases (suspect screening analysis [SSA]), or if no pre-knowledge matches, by elucidating the structure of unknowns using e.g. first order fragmentation (MS/MS) derived information matched to in silico predicted fragments from compound databases (non-targeted analysis [NTA]). It enables the simultaneous measurement and capability for semi-quantification of a large number of small molecules from samples using an unbiased approach.

If the focus is on the comparison of two or more aerosol samples, as described above, to evaluate any significant differences in chemical composition between samples in an unsupervised way or if group related pre-knowledge is available between sample groups, non-targeted differential screening (NTDS) may be performed. A complementary differential screening approach using liquid chromatography coupled to high-resolution accurate-mass mass spectrometry (LC-HRAM-MS) in parallel with two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) has been applied in order to ensure comprehensive analytical coverage for identifying the most relevant differences in aerosol composition between aerosols derived from articles comprising 100% by weight star anise as the particulate plant material and those derived from articles comprising 100% by weight tobacco as the particulate plant material.

The aerosol was generated and collected using the apparatus and methodology set out in detail below.

LC-HRAM-MS analysis was carried out using a Thermo QExactive™ high resolution mass spectrometer in both full scan mode and data dependent mode. In total, three different methods were applied in order to cover a wide range of substances with different ionization properties and compound classes. Samples were analysed using RP chromatography with heated electrospray ionisation (HESI) in both positive and negative modes and with atmospheric pressure chemical ionisation (APCI) in positive mode. The methods are described in: Arndt, D. et al, “In depth characterization of chemical differences between heat-not-burn tobacco products and cigarettes using LC-HRAM-MS-based non-targeted differential screening” (DOI:10.13140/RG.2.2.11752.16643); Wachsmuth, C. et al, “Comprehensive chemical characterisation of complex matrices through integration of multiple analytical modes and databases for LC-HRAM-MS-based non-targeted screening” (DOI: 10.13140/RG.2.2.12701.61927); and “Buchholz, C. et al, “Increasing confidence for compound identification by fragmentation database and in silico fragmentation comparison with LC-HRAM-MS-based non-targeted screening of complex matrices” (DOI: 10.13140/RG.2.2.17944.49927), all from the 66th ASMS Conference on Mass Spectrometry and Allied Topics, San Diego, USA (2018). The methods are further described in: Arndt, D. et al, “A complex matrix characterization approach, applied to cigarette smoke, that integrates multiple analytical methods and compound identification strategies for non-targeted liquid chromatography with high-resolution mass spectrometry” (DOI: 10.1002/rcm.8571).

GC×GC-TOFMS analysis was carried out using an Agilent GC Model 6890A or 7890A Instrument equipped with an Auto Liquid Injector (Model 7683B) and a Thermal Modulator coupled to a LECO Pegasus 4D™ mass spectrometer with three different methods for nonpolar, polar and highly volatile compounds within the aerosol. The methods are described in: Almstetter et al, “Non-targeted screening using GC×GC-TOFMS for in-depth chemical characterization aerosol from a heat-not-burn tobacco product” (DOI: 10.13140/RG.2.2.36010.31688/1); and Almstetter et al, “Non-targeted differential screening of complex matrices using GC×GC-TOFMS for comprehensive characterization of the chemical composition and determination of significant differences” (DOI: 10.13140/RG.2.2.32692.55680), from the 66th and 64th ASMS Conferences on Mass Spectrometry and Allied Topics, San Diego, USA, respectively.

The results from the analysis methods provided information regarding the major compounds responsible for the differences in the aerosols generated by such articles. The focus of the non-targeted differential screening using both analytical platforms LC-HRAM-MS and GC×GC-TOFMS was on compounds that were present in greater amounts in the aerosols of a sample of an aerosol-generating substrate according to the invention comprising 100 percent star anise particles relative to a comparative sample of an aerosol-generating substrate comprising 100 percent tobacco particles. The NTDS methodology is described in the papers listed above.

Based on this information, the inventors were able to identify specific compounds within the aerosol that may be considered as “characteristic compounds” deriving from the star anise particles in the substrate. Characteristic compounds unique to star anise include but are not limited to: (E)-anethole, epoxyanethole and benzyl isoeugenol ether. For the purposes of the present invention, a targeted screening can be conducted on a sample of aerosol-generating substrate to identify the presence and amount of each of the characteristic compounds in the substrate. Such a targeted screening method is described below. As described, the characteristic compounds can be detected and measured in both the aerosol-generating substrate and the aerosol derived from the aerosol-generating substrate.

As defined above, the aerosol-generating article of the invention comprises an aerosol-generating substrate formed of a homogenised star anise material comprising star anise particles. As a result of the inclusion of the star anise particles, the aerosol-generating substrate comprises certain proportions of the “characteristic compounds” of star anise, as described above. In particular, the aerosol-generating substrate comprises at least about 70 micrograms of (E)-anethole per gram of the substrate, at least about 50 micrograms of epoxyanethole per gram of the substrate and at least about 130 micrograms of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

By defining an aerosol-generating substrate with respect to the desired levels of the characteristic compounds, it is possible to ensure consistency between products despite potential differences in the levels of the characteristic compounds in the raw materials. This advantageously enables the quality of the product to be controlled more effectively.

Preferably, the aerosol-generating substrate comprises at least about 0.75 mg of (E)-anethole per gram of the substrate, more preferably at least about 1.5 mg of (E)-anethole per gram of the substrate, on a dry weight basis. Alternatively or in addition, the aerosol-generating substrate preferably comprises no more than about 3 mg of (E)-anethole per gram of the substrate, more preferably no more than about 2.5 mg of (E)-anethole per gram of the substrate and more preferably no more than about 2.2 mg of (E)-anethole per gram of the substrate. For example, the aerosol-generating substrate may comprise between about 70 micrograms and about 3 mg (E)-anethole per gram of the substrate, or between about 0.75 mg and about 2.5 mg (E)-anethole per gram of the substrate, or between about 1.5 mg and about 2.2 mg (E)-anethole per gram of the substrate, on a dry weight basis.

Preferably, the aerosol-generating substrate comprises at least about 0.75 mg of epoxyanethole per gram of the substrate, more preferably at least about 1.5 mg of epoxyanethole per gram of the substrate, on a dry weight basis. Alternatively or in addition, the aerosol-generating substrate preferably comprises no more than about 3 mg of epoxyanethole per gram of the substrate. more preferably no more than about 2.5 mg of epoxyanethole per gram of the substrate and more preferably no more than about 2 mg of epoxyanethole per gram of the substrate. For example, the aerosol-generating substrate may comprise between about 50 micrograms and about 3 mg epoxyanethole per gram of the substrate, or between about 0.75 mg and about 2.5 mg epoxyanethole per gram of the substrate, or between about 1.5 mg and about 2 mg epoxyanethole per gram of the substrate, on a dry weight basis.

Preferably, the aerosol-generating substrate comprises at least about 1 mg of benzyl isoeugenol ether per gram of the substrate, more preferably at least about 2 mg of benzyl isoeugenol ether per gram of the substrate, on a dry weight basis. Alternatively or in addition, the aerosol-generating substrate preferably comprises no more than about 5 mg of benzyl isoeugenol ether per gram of the substrate, more preferably no more than about 4.5 mg of benzyl isoeugenol ether per gram of the substrate and more preferably no more than about 4 mg of benzyl isoeugenol ether per gram of the substrate. For example, the aerosol-generating substrate may comprise between about 130 micrograms and about 5 mg benzyl isoeugenol ether per gram of the substrate, or between about 1 mg and about 4.5 mg benzyl isoeugenol ether per gram of the substrate, or between about 2 mg and about 4 mg benzyl isoeugenol ether per gram of the substrate, on a dry weight basis.

Preferably, the ratio of the characteristic compounds in the aerosol-generating substrate is such that the amount of (E)-anethole per gram of the substrate is no more than 5 times the amount of epoxyanethole per gram of the substrate. more preferably no more than 3 times the amount of epoxyanethole per gram of the substrate, on a dry weight basis. This ratio of (E)-anethole to epoxyanethole is significantly lower than the corresponding ratio in star anise oil and is characteristic of the inclusion of star anise particles in the aerosol-generating substrate. In contrast, star anise oil typically comprises no more than a trace amount of epoxyanethole and a relatively high proportion of (E)-anethole.

Alternatively or in addition, the amount of benzyl isoeugenol ether per gram of the substrate is preferably at least 1.5 times the amount of (E)-anethole per gram of the substrate, preferably at least 1.75 times the amount of (E)-anethole per gram of the substrate, on a dry weight basis. The presence of benzyl isoeugenol ether at a higher level than (E)-anethole is characteristic of the inclusion of star anise particles. In contrast, star anise oil typically comprises no more than a trace amount of benzyl isoeugenol ether and a relatively high proportion of (E)-anethole.

As defined above, the invention also provides an aerosol-generating article that comprises an aerosol-generating substrate formed of a homogenised plant material comprising star anise particles, wherein upon heating of the aerosol generating substrate, an aerosol is generated which comprises the “characteristic compounds” of star anise.

For the purposes of the invention, the aerosol-generating substrate is heated according to “Test Method A”. In Test Method A, an aerosol-generating article incorporating the aerosol-generating substrate is heated in a Tobacco Heating System 2.2 holder (THS2.2 holder) under the Health Canada machine-smoking regimen. For the purposes of carrying out Test Method A, the aerosol-generating substrate is provided in an aerosol-generating article that is compatible with the THS2.2 holder.