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Over the last decade, numerous research efforts have been devoted to pillar[n]arenes since their debut. The popularity of pillararenes is a reflection of current research trend in supramolecular and macrocyclic chemistry in general. Among the vast applications (such as chemosensors, drug delivery, transmembrance channels, and separation) of pillararenes, their utilization in catalysis is a relatively less explored area. However, soaring attention has been paid by researchers in recent years and this field has seen gradual increasing publications. Therefore, in this review we will discuss progress in the emerging applications of pillararene architectures in catalysis based on various reaction genre including reduction, oxidation, coupling, decomposition and others. Furthermore, this review not only focuses on the pillararenes based current progress in catalysis, but also provides the signs for future development in this research field.

Here we describe the synthesis and characterization of a peptide-cellulose conjugate biosensor based on TEMPO-oxidized nanofibrillated cellulose (tNFC) for detecting elevated levels of human neutrophil elastase (HNE) in chronic wounds. The fluorescent peptide HNE substrate constructed from n-succinyl-Ala-Pro-Ala-7-amino-4-methyl-coumarin was attached to the TEMPO-oxidized cellulose surface via polyethylene glycol linker. The characterization of the biosensor conjugate shows a high degree of peptide incorporation onto the surface with the degree of substitution of 0.057. The relatively small crystallite size of 26.0 Å compared to other cellulose- and nanocellulose-based materials leads to a large specific surface area which can promote access of HNE to the enzyme substrates due to decreased steric interactions. Likewise, the porosity for tNFC was found to be higher than all other samples, including the nanocellulosic aerogel, lending to its hydrogel-like nature. The properties of tNFC were compared to other cellulose-based materials. The volume of each crystallite and volume ratio to the largest sample was calculated. tNFC was found to occupy the smallest space resulting in high amounts of sensors per crystallite unit volume. With a small crystallite volume and large number of sensors, the tNFC peptide-cellulose conjugate biosensor could provide a more sensitive system and is a good candidate for point of care diagnostic devices for detecting elevated protease levels in humans.

There are many open questions regarding the supramolecular properties of ions in water, a fact that has ramifications within any field of study involving buffered solutions. Indeed, as Pielak has noted (Buffers, Especially the Good Kind, Biochemistry, 2021, in press. DOI:10.1021/acs.biochem.1c00200) buffers were conceived of with little regard to their supramolecular properties. But there is a difficulty here; the mathematical models supramolecular chemists use for affinity determinations do not account for screening. As a result, there is uncertainty as to the magnitude of any screening effect and how this compares to competitive salt/buffer binding. Here we use a tetra-cation cavitand to compare halide affinities obtained using a traditional unscreened model and a screened (Debye–Hückel) model. The rule of thumb that emerges is that if ionic strength is changed by >1 order of magnitude—either during a titration or if a comparison is sought between two different buffered solutions—screening should be considered. We also build a competitive mathematical model showing that binding attenuation in buffer is largely due to competitive binding to the host by said buffer. For the system at hand, we find that the effect of competition is approximately twice that of the effect of screening (∼RT at 25 °C). Thus, for strong binders it is less important to account for screening than it is to account for competitive complexation, but for weaker binders both effects should be considered. We anticipate these results will help supramolecular chemists unravel the properties of buffers and so help guide studies of biomacromolecules.

The many useful features possessed by pillararenes (PAs; e.g. rigid, capacious, and hydrophobic cavities, as well as exposed functional groups) have led to a tremendous increase in their popularity since their first discovery in 2008. In this Minireview, we emphasize the use of functionalized PAs and their assembled supramolecular materials in the field of catalysis. We aim to provide a fundamental understanding and mechanism of the role PAs play in catalytic process. The topics are subdivided into catalysis promoted by the PA rim/cavity, PA-based nanomaterials, and PA-based polymeric materials. To the best of our knowledge, this is the first overview on PA-based catalysis. This Minireview not only summarizes the fabrications and applications of PAs in catalysis but also anticipates future research efforts in applying supramolecular hosts in catalysis.

The use of agricultural waste and residues in composite materials is a potential high-value commercial application for underutilized renewable resources and provides alternative commercial markets to the agricultural industry. Cotton gin trash (CGT) and cotton gin motes (CGM) are underutilized low-value commodities that are attractive targets due to their high cellulose content; however, each contains various amounts of lignin, hemicellulose and other components that impede their utilization as commercial products. In this work, lignin-containing cellulose nanofibers (LCNFs) with gradient degrees of lignin content were prepared from CGT and CGM. Analyses showed the lignin content and other components affected the physical properties of LCNFs, modestly altering their thermal stability and crystallinity. The degree of polymerization (DP) was smaller after successive rounds of processing and was also dependent upon the source (CGT or CGM) with CGT providing nanofibers with a smaller DP than CGM. This translated into slightly different suspension viscoelastic behavior as determined by rheological measurements.

A simple method was developed to deposit palladium (Pd) nanoparticles (NPs) within an inexpensive substrate, nonwoven brown cotton fabric, using naturally occurring polyphenols contained within the...

Science still does not have the ability to accurately predict changes in ligand affinity induced by proximal charged groups., Science still does not have the ability to accurately predict the affinity that ligands have for proteins. In an attempt to address this, the Statistical Assessment of Modeling of Proteins and Ligands (SAMPL) series of blind predictive challenges is a community-wide exercise aimed at advancing computational techniques as standard predictive tools in rational drug design. In each cycle, a range of biologically relevant systems of different levels of complexity are selected to test the latest modeling methods. As part of this on-going exercise, and as a step towards understanding the important factors in context dependent guest binding, we challenged the computational community to determine the affinity of a series of negatively and positively charged guests to two constitutionally isomeric cavitand hosts: octa-acid 1, and exo-octa acid 2. Our affinity determinations, combined with molecular dynamics simulations, reveal asymmetries in affinities between host–guest pairs that cannot alone be explained by simple coulombic interactions, but also point to the importance of host–water interactions. Our work reveals the key facets of molecular recognition in water, emphasizes where improvements need to be made in modelling, and shed light on the complex problem of ligand-protein binding in the aqueous realm.

Cellulose nanocrystals (CNC) have attracted a great deal of attention as an environmentally-friendly biorenewable resource for use as reinforcing agents in nanocomposites, polymers, gels, and emulsions. CNCs are typically prepared from extracted cellulose or highly refined cellulose products. The chemical refining process can alter the chemical and physical properties of the cellulose fibers prior to extraction of CNCs. Moreover, the method of isolation can also insert various functional groups onto the nanocellulose, affecting thermal stability and imparting different physical properties. Herein, two byproducts of the cotton industry, cotton gin motes and cotton gin waste, are investigated for the preparation of nanocelluloses. Cellulose was purified from these two post-process agroindustrial by-products and CNCs subsequently produced by sulfuric acid hydrolysis. Additionally, two acid hydrolysis methods were utilized to successfully extract CNCs from gin motes without chemical pretreatment. CNCs were obtained with diameters

We describe the use of a supramolecular nano-capsule for selective protection of cis- and trans-C18 mono-unsaturated fatty-acid esters. In contrast to earlier studies revealing that protection of smaller esters is dictated by affinity, protection of these larger esters was found to be dependent on the packing motif of the guest.

Controlling the self-assembly of molecules in water is difficult because the small size, polarity, and hydrogen bond donating and accepting properties of water attenuate most non-covalent interactions. Here we describe how resorcinarene 1, with pyridinium pendent groups, assembles in water to form head-to-tail assemblies. These small supramolecular polymers form because they offer greater stabilization than any latent head-to-head assembly of resorcinarenes to form dimeric (or hexameric) containers. Instead, the resorcinarene bowl – particularly if negatively charged – is a good host for the pyridinium pendent groups of a second resorcinarene. Alternatively, resorcinarene 1 is also a good host for complexing anions and cations of any added salt. In combination therefore, host 1 possesses a rich repertoire of supramolecular properties that is dependent on the ionic strength and the nature of salts, pH, and the concentration of the host. These findings provide new information about controlling the self-assembly of resorcinarenes in water.

Azo dyes are commonly used in textile color processing for their wide array of vibrant colors. However, in recent years these dyes have become of concern in wastewater management given their toxicity to humans and the environment. In the present work, researchers remediated water contaminated with azo dyes using silver nanoparticles (Ag NPs) intercalated within cotton fabric as a catalyst, for their enhanced durability and reusability, in a reductive degradation method. Three azo dyes—methyl orange (MO), Congo red (CR), and Chicago Sky Blue 6B (CSBB)—were investigated. The azo degradation was monitored by UV/vis spectroscopy, degradation capacity, and turnover frequency (TOF). The Ag NP–cotton catalyst exhibited excellent degradation capacity for the dyes, i.e., MO (96.4% in 30 min), CR (96.5% in 18.5 min), and CSBB (99.8% in 21 min), with TOFs of 0.046 min−1, 0.082 min−1, and 0.056 min−1, respectively, using a 400 mg loading of catalyst for 100 mL of 25 mg L−1 dye. To keep their high reusability while maintaining high catalytic efficiency of >95% degradation after 10 cycles, Ag NPs immobilized within cotton fabric have promising potential as eco-friendly bio-embedded catalysts.

Lymphotoxin alpha (LTα) plays an important role in lymphoid organ development and cellular cytotoxicity in the immune system. LTα expression is increased in the cerebrospinal fluid of naïve and progressive multiple sclerosis (MS) patients and post-mortem meningeal tissue. Here we show that persistently increased levels of LTα in the cerebral meninges can give rise to lymphoid-like structures and underlying MS-like cortical pathology. Stereotaxic injections of recombinant LTα into the rat meninges leads to acute meningeal inflammation and subpial demyelination that resolves after 28 days. Injection of an LTα lentiviral vector induces lymphoid-like immune cell aggregates, maintained over 3 months, including T-cell rich zones containing podoplanin+ fibroblastic reticular stromal cells and B-cell rich zones with a network of follicular dendritic cells, together with expression of lymphoid chemokines and their receptors. Extensive microglial activation, subpial demyelination and marked neuronal loss occurs in the underlying cortical parenchyma. These results show that chronic LTα overexpression is sufficient to induce formation of meningeal lymphoid-like structures and subsequent neurodegeneration.SummaryIncreased release of lymphotoxin-alpha contributes to the pro-inflammatory milieu of the cerebrospinal fluid of MS patients. A persistent elevated expression of this cytokine in the meninges of rats gives rise to chronic inflammation with lymphoid tissue induction and accompanying neurodegenerative and demyelinating pathology in the underlying brain tissue.

The preparation of cellulose nanocrystals (CNCs) from cellulose extracted from cotton gin motes (CGM) using an ionic liquid (1-butyl-3-methylimidazolium chloride, [BMIm]Cl) under dilute conditions is reported. The concurrent process involves minimal swelling of cellulose with an ionic liquid and hydrolysis of the cellulose initiated by the addition of either phosphoric (H3PO4), hydrochloric (HCl), or sulfuric (H2SO4) acid. The obtained nanocrystals had similar physical properties (e.g. crystallinity) to the counterparts prepared under conventional conditions and exhibited superior thermal properties for sulfate CNCs. Additionally, the obtained CNCs had low surface functionalization, yet were colloidally stable for >90 days, which is a desirable trait for post-functionalization of CNCs. This process represents a general strategy utilizing dilute ionic liquids in the preparation of nanocellulose under mildly acidic conditions.

Nanospaces are ubiquitous in the realm of biological systems and are of significant interest among supramolecular chemists. Understanding chemical behavior within nanospaces offers new perspectives on biological phenomena in nature and opens the way to highly unusual and selective forms of catalysis. Supramolecular chemistry exploits weak, yet effective, intermolecular interactions such as hydrogen bonding, metal-ligand coordination, and the hydrophobic effect to assemble nano-sized molecular architectures, providing reactions with remarkable rate acceleration, substrate specificity, and product selectivity. In this minireview, the focus is on the strategies that supramolecular chemists use to emulate the efficiency of biological processes, and elucidating how chemical reactivity is efficiently controlled within well-defined nanospaces. Approaches such as orientation and proximity of substrate, transition-state stabilization, and active-site incorporation will be discussed.

A combination of 1H NMR spectroscopy, DLS, and turbidity measurements reveal that polarizable anions engender both the Hofmeister and reverse Hofmeister effects in positand 2. Host 2 possesses two principal and distinctly different binding sites: a “soft” nonpolar pocket and a “hard” crown of ammonium cations. NMR spectroscopy reveals that anion affinity to both sites is comparable, with each site showing characteristic selectivities. NMR spectroscopy also reveals that anions competitively bind to the pocket and induce the Hofmeister effect in host–guest binding at very low concentrations (∼2 mM). Furthermore, the suite of techniques utilized demonstrates that anion binding to both sites leads to charge attenuation, aggregation, and finally precipitation (the reverse Hofmeister effect). Anion-induced precipitation generally correlated with affinity, and comparisons between the free host and its adamantane carboxylate (Ada-CO2–) complex reveals that the reverse Hofmeister effect is attenuated by blocking a...

Cellulose nanocrystals (CNCs) are a biorenewable resource, which may be chemically modified to impart specific properties. Modified CNCs have found use in imaging applications, as rheology modifiers, polymer reinforcements, barrier and/or optical films, and nanocomposites. Nanoparticle dimensions of CNCs are typically 5&ndash, 10 nm in width, with lengths of &lt, 100&ndash, 300 nm. However, the physical properties are dependent upon the number and nature of the surface charge groups imparted during preparation. In the case of CNCs produced from sulfuric acid hydrolysis, the sulfated surface groups may be partially removed prior to further functionalization. This gives more available hydroxyls yet renders the CNCs less colloidally stable. Furthermore, conditions vary significantly and there is no consensus about the optimal conditions for partial removal of sulfate functionality or conditions developed to give specific surface charge. In the following, alkali hydrolysis of sulfate half-esters was quantified by conductometric titration of the strong acid groups, and using a design of experiments (DOE), optimal conditions were determined to produce CNCs with tailored surface charge.

Bisphenol-substituted spirocyclic phosphazene derivatives were synthesized in 85%–94% yields and analyzed for flame retardant application to cotton fabric using Limiting Oxygen Index, Fourier transform infrared thermogravimetric analysis, differential scanning calorimetry, microscale combustion calorimetry, thermogravimetric analysis, and scanning electron microscopy. The thermogravimetric analysis methods indicate a decomposition pathway consistent for phosphorus-nitrogen-containing compounds. Levoglucosan phosphorylation and carbonaceous char formation were observed. Limiting Oxygen Index testing of these compounds on cotton-based fabrics showed improved flame resistance compared to untreated fabrics.

There are several classes of water-soluble host molecules that are of current interest: cyclodextrins, cucurbiturils, calixarenes, resorcinarenes and derived cavitands, and most recently pillarenes. This article focuses on just one of these: water-soluble cavitands based on the resorcinarene scaffold. In contrast to cyclodextrins, cucurbiturils, and pillarenes, these cavitands possess rigidly enforced concavity (negative curvature) for guest binding. Along with suitable functionalization bestowing water solubility, these hosts offer a unique perspective of supramolecular chemistry in aqueous solution. Using selected examples, this article examines the general strategies behind cavity formation and the most common approaches to water solubilization. Selected examples are also used to highlight applications of these unique water-soluble hosts.

An efficient, four-step synthesis of a range of water-soluble, deep-cavity cavitands is presented. Key to this approach are octahalide derivatives (4, X = Cl or Br) that allow a range of water-solubilizing groups to be added to the outer surface of the core host structure. In many cases, the conversion of the starting dodecol (1) resorcinarene to the different cavitands avoids any chromatographic procedures.

Lysine-containing polymers have seen broad application due to their amines' inherent ability to bind to a range of biologically relevant molecules. The synthesis of multiple generations of polyester dendrimers bearing lysine groups on their periphery is described in this report. Their hydrolytic stabilities with respect to pH and time, their toxicity to a range of cell lines, and their possible application as nano-detoxification agents of organophosphate compounds are all investigated. These zeroth-, first-, and second-generation water-soluble dendrimers have been designed to bear exactly 4, 8, and 16 lysine groups, respectively, on their dendritic periphery. Such monodisperse bioactive polymers show potential for a range of applications including drug delivery, gene delivery, heavy metal binding, and the sequestration of organic toxins. These monodisperse bioactive dendrimers were synthesized using an aliphatic ester dendritic core (prepared from pentaerythritol) and protected amino acid moieties. This library of lysine-conjugated dendrimers showed the ability to efficiently capture the pesticide dichlorvos, confirming the potential of dendrimer-based antidotes to maintain acetylcholinesterase activity in response to poisoning events.

This review focuses on molecular containers formed by assembly processes driven by the hydrophobic effect, and summarizes the progress made in the field over the last ten years. This small but growing facet of supramolecular chemistry discusses three classes of molecules used by researchers to investigate how self-assembly can be applied to form discrete, mono-dispersed, and structurally well-defined supramolecular entities. The approaches demonstrate the importance of preorganization of arrays of rigid moieties to define a specific form predisposed to bind, fold, or assemble. As the examples demonstrate, studying these systems and their properties is teaching us how to control supramolecular chemistry in water, shedding light on aspects of aqueous solutions chemistry, and illustrating novel applications that harness the unique properties of the hydrophobic effect.

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Pachynematus clitellatus (SERVILLE, 1823) Dumfriesshire, White Coomb, 4 ♂♂, 19.vi.2010, leg. Liston. Treated in the sense of Taeger & Blank (1998). Male specimens from Meall nan Tarmachan, White Coomb and Corrie Fee, leg. Heibo and Liston key to P. kirbyi (Dahlbom, 1835) in Benson (1958) and might well be considered to represent a different species. These were swept from marshy land dominated by Carex, whilst P. clitellatus s. str. is also found on dry areas and is attached perhaps only to various Poaceae., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 42, {"references":["Taeger, A. & Blank, S. M. 1998: Beitrag zur Kenntnis einiger Nematinae (Hymenoptera: Tenthredinidae). pp. 247 - 277. - In: Taeger, A. & Blank, S. M. (eds) 1998: Pflanzenwespen Deutschlands (Hymenoptera, Symphyta). Kommentierte Bestandsaufnahme. - Goecke & Evers, Keltern: 1 - 364 + [3] pp.","Benson, R. B. 1958: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 c): 139 - 258."]}

Microdiprion pallipes (FALLÉN, 1808) Beinn Eighe NNR, NH0064, Wester Ross, native pinewood, 1 ♀, 11.v.-13.vi.1988, Malaise trap, leg. I. MacGowan (RSME). Both the above individuals (see also Table 1) are extremely pale. The lateral parts of the abdominal terga and most of the sterna are bright yellow. In the field, the Claybokie specimen was initially mistaken because of its pale colouration for Monoctenus juniperi (Linnaeus, 1758). However, the female of M. juniperi has at most a band of orange-brown along the lateral margins of the terga. Benson (1959) referred Scottish populations of M. pallipes to ssp. pallipes, found also from northern Fennoscandia south to around Berlin in Germany (Forsslund 1960). The nominate subspecies was considered to be replaced by M. pallipes ssp. politum (Klug, 1812), adults of which are much darker, in Alpine and pre-Alpine Europe. Mallach (1973) discussed some of the problems attached to the distinction of these putative subspecies. The description by Enslin (1917) of variability in colouration in Lophyrus (M.) pallipes still seems very fitting., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 40, {"references":["Benson, R. B. 1959: Sawflies (Hymenoptera, Symphyta) of Sutherland and Wester Ross. - Entomologist's Monthly Magazine 95: 101 - 104.","Forsslund, K. - H. 1960: Studier over lilla tallstekeln Diprion (Microdiprion) pallipes (Fall.). Studien uber die kleine Buschhornblattwespe Diprion (Microdiprion) pallipes (Fall.). - Meddelanden fran statens skogsforskningsinstitut 49: 1 - 62.","Mallach, N. 1973: Zur Kenntnis der Kleinen Kiefern-Buschhornblattwespe, Diprion (Microdiprion) pallipes (Fall.) (Hymenoptera, Diprionidae). Teil 1: Systematik, Verbreitung und Morphologie. - Zeitschrift fur angewandte Entomologie 74: 394 - 434.","Enslin, E. 1917: Die Tenthredinoidea Mitteleuropas VI. - Deutsche Entomologische Zeitschrift, Beiheft 6: 539 - 662."]}

Tenthredo mandibularis FABRICIUS, 1804 Edinburgh; Roseburn: 3 ♂♂, 16.vi.2010, leg. Liston; 1 ♀, 17.vi.2010, leg. Liston. Midlothian, Gorebridge, Gore Glen, 1 ♂, 18.vi.2010. Edinburgh, Juniper Green, W. of Leith, 1 ♀, 19.vi.2010, leg. Liston. Angus, 3 miles North of Kirriemuir, 2 ♂♂ (many more individuals seen, but only these two taken as vouchers), 23.vi.2010, leg. Liston (SDEI, RSME). These Scottish adults were collected exclusively from stands of Petasites hybridus, which seems likely to be the larval host. According to Benson (1952) Tenthredo mandibularis is “Recorded from Dorset, Hants., Essex, Kent, Beds., Oxon., Yorks., and Cheshire. Probably occurs wherever the Petasites is abundant in England.” No previous records from Scotland of this conspicuous and distinctive species are known. Published hostplant records refer only to Petasites, usually without naming a species (Lorenz & Kraus 1957), or identify only P. albus as a host (Pschorn-Walcher & Altenhofer 2000). According to observations apparently made only by Brischke (1883), but often repeated in subsequent publications without citation of the source, Petasites officinalis (a synonym of P. hybridus) and Tussilago farfara are hosts. Tussilago farfara is the main or only host of T. mandibularis in Norway according to Heibo & Lönnve (2005)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on pages 54-55, {"references":["Benson, R. B. 1952: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 b): 51 - 137.","Lorenz, H. & Kraus, M. 1957: Die Larvalsystematik der Blattwespen (Tenthredinoidea und Megalodontoidea). - Abhandlungen zur Larvalsystematik der Insekten 1: 1 - 389.","Pschorn-Walcher, H. & Altenhofer, E. 2000: Langjahrige Larvenaufsammlungen und Zuchten von Pflanzenwespen (Hymenoptera, Symphyta) in Mitteleuropa. - Linzer biologische Beitrage 32: 273 - 327.","Brischke, C. G. A. 1883: Beobachtungen uber die Arten der Blatt- und Holzwespen von C. G. A. Brischke, Hauptlehrer a. D. in Langfuhr und Dr. Gustav Zaddach weiland Professor in Konigsberg. Zweite Abtheilung. - Schriften der Naturforschenden Gesellschaft in Danzig 5: 201 - 328.","Heibo, E. & Lonnve, O. J. 2005: Tenthredo amoena Gravenhorst, 1807, T. mandibularis Fabricius, 1804 and Rhogogaster californica (Norton, 1872) (Hymenoptera, Symphyta, Tenthredinidae) in Norway. - Norwegian Journal of Entomology 52: 145 - 149."]}

Nematus frenalis THOMSON, 1888 Ben Vraikie (1150ft), near Moulin, 1 ♂, 8.vi.2010, leg. Halstead. There are only two previous British records (Benson 1958, Speyside; Liston 1981b, Lanarkshire)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 40, {"references":["Benson, R. B. 1958: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 c): 139 - 258.","Liston, A. D. 1981 b: Loderus gilvipes (Klug) in Scotland, with second British records of Pristiphora bifida Hellen and Nematus frenalis Thomson (Hymenoptera, Tenthredinidae). - Entomologist's Record and Journal of Variation, London 93: 222 - 223."]}

Parna apicalis (BRISCHKE, 1888) Malleny Woods and Colinton Dell; several leaf-mines on Common Lime (T. x vulgaris Heyne), 19.vi.2010, leg. Liston. Most vacated, but 2 still with larvae. Parna apicalis was first recorded as a British species by Edmunds et al. (2007), but perhaps was previously overlooked, rather than being a very recently introduced species. Both Dr M. R. Shaw (pers. comm.) and Liston probably observed the characteristic leaf-mines in the Edinburgh area as early as the 1980’s, but at the time attributed these to Parna tenella (Klug, 1816)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 42, {"references":["Edmunds, R.; Hind, S.; Liston, A. D. & Palmer, K. 2007: Parna apicalis (Brischke, 1888) (Symphyta: Tenthredinidae), a Leaf-mining Sawfly New to Great Britain. - Entomologist's Record and Journal of Variation 119: 223 - 226."]}

Empria basalis LINDQVIST, 1968 Empria basalis was recorded as new to Britain, based on specimens from Cumbria, by Knight (2009a). The only known hostplant is Geum rivale (Prous et al. 2011)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 36, {"references":["Knight, G. T. 2009 a: Empria basalis Lindqvist, 1968 - a new sawfly to Britain. - Sawfly Study Group Newsletter 4: 15 - 16.","Prous, M.; Heidemaa, M. & Soon, V. 2011: Empria longicornis species group: taxonomic revision with notes on phylogeny and ecology (Hymenoptera, Tenthredinidae). - Zootaxa 2756: 1 - 39."]}

Nematus leionotus (BENSON, 1933) Shieldaig, Wester Ross, NG 8252, native pinewood, 1 ♀, v.1991, Malaise trap, I. MacGowan (RSME). Only one previous published record in Scotland (Liston 1980a; E. Lothian)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 41, {"references":["Liston, A. D. 1980 a: Notes on sawflies (Hymenoptera, Symphyta) collected in Scotland. - Entomologist's Monthly Magazine 115 (1979): 239 - 243."]}

Cladius ulmi (LINNAEUS, 1758) Malleny Woods, 1 ♀, 12.vi.2010, leg. Liston. Cladius ulmi has only been recorded once before in Scotland, from Fife (Liston 1982a)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 34, {"references":["Liston, A. D. 1982 a: Two southern sawflies (Hymenoptera, Tenthredinidae) from Loch Leven NNR, Fife, Scotland. - Entomologist's Monthly Magazine 118: 119."]}

Pachynematus clibrichellus (CAMERON, 1878) Dumfriesshire, White Coomb, north of summit, ca 750 m, 1 ♂, 19.vi.2010, leg. Liston. Recorded by Benson (1958) from “Perths., Inverness, Angus, Sutherland and Caithness, mostly on mountain tundra, but at sea level at Wick in Caithness[..]”, but also found by Nelson (1971) at high altitudes in the northern Pennines of England. It is therefore of little surprise that Pachynematus clibrichellus has now been found on one of the highest hills in the Southern Uplands of Scotland, where a few other very local occurrences of ‘arctic-alpine’ sawfly species are already known (Liston 1983b; 1984, record refers to Pontania herbaceae)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 41, {"references":["Cameron, P. 1878: The fauna of Scotland, with special reference to Clydesdale and the Western District. Hymenoptera. Part I. - Proceedings (& Transactions) of the Natural History Society of Glasgow 3 (Suppl.): 1 - 52.","Benson, R. B. 1958: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 c): 139 - 258.","Nelson, J. M. 1971: The Invertebrates of an Area of Pennine Moorland within the Moor House Reserve in Northern England. - Transactions of the Society of British Entomology 19: 173 - 235.","Liston, A. D. 1983 b: Some northern and arctic-alpine sawflies (Hymenoptera, Tenthredinidae) from the Scottish Southern Uplands. - Entomologist's Monthly Magazine 119: 67 - 70.","Liston, A. D. 1984: A thriving population of Pontania crassipes (Thomson) (Hymenoptera, Tenthredinidae) in southern Scotland. - Entomologist's Record and Journal of Variation 96: 181 - 182."]}

Empria tridens (KONOW, 1896) Baddoch, 1 ♀, 04.vi.2010, leg. Blank, Liston & Taeger, det. M. Prous. The Kindrogan individual (SDEI-GISHym14894), with peculiar morphology of the head (Fig. 7; strongly inflated towards the rear, with small eyes), was mentioned by Prous et al. (2011). Other characters, including the morphology of the saw (http://www.morphbank.net/?id=588539), are not distinguishable from E. tridens (Konow, 1896). According to molecular data, the specimen is not remarkable (see Prous et al. (2011, particularly Fig. 18). Mitochondrial DNA of the specimen is very similar to a group of sequences comprising mainly E. tridens and E. basalis (see Fig. 20 in Prous et al., 2011). This individual is at present most conveniently considered to be a developmental [teratological] abnormality. However, a female E. tridens with a head very similar to the Kindrogan specimen has also been collected by Knight in Cumbria. The existence of two such specimens indicates a need to try to exclude other possible causes of the abnormality. Alternative causes are for example pathological (e.g. infection of the pharyngeal glands by a nematode). The habit of mature larvae of Empria species (and many other Allantinae) of boring into substrates such as rotten wood, rich in nematode species that are known to infect the postpharyngeal glands of ants (Wheeler 1928), might expose them (or the prepupal and pupal stages) to such infection (by anology with infection of ants, perhaps in the salivary glands of sawflies?). So it may be worth noting that pupation of Empria species is in a cell in the substrate, lacking any clearly identifiable cocoon and thereby increasing the vulnerability of prepupae and / or pupae to nematode infection., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 37, {"references":["Prous, M.; Heidemaa, M. & Soon, V. 2011: Empria longicornis species group: taxonomic revision with notes on phylogeny and ecology (Hymenoptera, Tenthredinidae). - Zootaxa 2756: 1 - 39.","Wheeler, W. M. 1928: Mermis parasitism and intercastes among ants. - The Journal of Experimental Zoology 50: 165 - 237."]}

Sciapteryx soror KONOW, 1890 Orkney, Hoy, Nowt Bield, HY 2301 (111), 21.vi.2009 (2), leg. Bland, det. Liston. Orkney, Hoy, Quoyberstane, HY 4612 (111), 22.vi.2009 (2), leg. Bland, det. Liston. An addition to the list of Orkney sawflies (Liston 1983c, Sheppard 1986). Note that Blank & Taeger (1998) treated S. soror provisionally as an Atlantic subspecies of the more continental S. costalis (Fabricius, 1775), but mentioned that they may be found to be synonyms when a greater amount of material from throughout Europe becomes available for comparison. Sciapteryx species are typically active in the early spring. Benson (1952) gives April to May as the flight period of S. soror, that he recorded “N. to Aberdeen and Inverness”. The records above are surprisingly late, even though they represent the most northerly known occurrences in the entire range of S. soror (Taeger et al. 2006)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 52, {"references":["Liston, A. D. 1983 c: Sawflies (Hymenoptera) from the Orkney Islands. - Entomologist's Gazette 34: 113 - 115.","Sheppard, D. A. 1986: Sawflies (Hymenoptera) from the Island of Hoy, Orkney. - Entomologist's Gazette 37: 99 - 100.","Taeger, A. & Blank, S. M. 1998: Beitrag zur Kenntnis einiger Nematinae (Hymenoptera: Tenthredinidae). pp. 247 - 277. - In: Taeger, A. & Blank, S. M. (eds) 1998: Pflanzenwespen Deutschlands (Hymenoptera, Symphyta). Kommentierte Bestandsaufnahme. - Goecke & Evers, Keltern: 1 - 364 + [3] pp.","Benson, R. B. 1952: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 b): 51 - 137.","Taeger, A.; Blank, S. M. & Liston, A. D. 2006: European Sawflies (Hymenoptera: Symphyta) - A Species Checklist for the Countries. pp 399 - 504. - In: Blank, S. M.; Schmidt, S. & Taeger, A. (eds) Recent Sawfly Research: Synthesis and Prospects. Keltern: Goecke & Evers."]}

Dolerus brevicornis ZADDACH, 1859 Baddoch, 1 ♀, 4.vi.2010, leg. Blank, Liston & Taeger. Dolerus brevicornis was only recently distinguished from D. asper Zaddach, 1859 (Heidemaa et al. 2004). Both species occur in the British Isles, but their distribution needs clarification. The above records are the first of D. brevicornis from Scotland., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 35, {"references":["Heidemaa, M.; Nuorteva, M.; Hantula, J. & Saarma, U. 2004: Dolerus asper Zaddach, 1859 and Dolerus brevicornis Zaddach, 1859 (Hymenoptera: Tenthredinidae), with notes on their phylogeny. - European Journal of Entomology 101: 637 - 650."]}

Tenthredo moniliata KLUG, 1817 Orkney, Hoy, Quoyberstane, HY 4612 (111), 1 ♀, 22.vi.2009, leg. Bland, det. Liston. Malleny Woods, (artificial?) pond, 1 ♀, 12.vi.2010, leg. Liston. As noted by Benson (1952), Tenthredo moniliata is in the British Isles exclusively associated with Menyanthes trifoliata L. [see also above under T. ignobilis]. In the Highlands T. moniliata is widespread, although not previously recorded in Orkney. Around Edinburgh and in other areas of the British mainland south of the Highlands it has become restricted to a very few sites (except in Wales, where it is local but widespread, as in Ireland). Its sole host has suffered numerous local extinctions, as for example is well documented in the Edinburgh area: compare Martin (1934) with BSBI (2010). The colour form with mainly black femora decribed by Cameron (1878) as T. lachlaniana falls within our present concept of variability in T. moniliata. The status of T. moniliata as regionally endangered in lowland Britain is similar to its status in the lowlands of Central Europe, but in Austria and Germany the situation is complicated by the existence of populations (or perhaps as yet undistinguished sibling species) on Origanum and Pulsatilla., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 55, {"references":["Klug, F. 1817: Die Blattwespen nach ihren Gattungen und Arten zusammengestellt. - Der Gesellschaft Naturforschender Freunde zu Berlin Magazin fur die neuesten Entdeckungen in der gesamten Naturkunde 8: 179 - 219.","Benson, R. B. 1952: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 b): 51 - 137.","Martin, I. H. (ed.) 1934: The Field-Club Flora of The Lothians. - Edinburgh & London: Blackwood.","BSBI [Botanical Society of the British Isles] 2010: Maps Scheme. http: // www. bsbimaps. org. uk. / atlas / atlas _ abspecies _ select. php [accessed 16. viii. 2010]","Cameron, P. 1878: The fauna of Scotland, with special reference to Clydesdale and the Western District. Hymenoptera. Part I. - Proceedings (& Transactions) of the Natural History Society of Glasgow 3 (Suppl.): 1 - 52."]}

Athalia liberta (KLUG, 1815) Edinburgh, Roseburn, Water of Leith, 1 ♀, 17.vi.2010, leg. Liston. In Scotland Alliaria petiolata is the main [possibly only?] host., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 33

Dolerus gessneri ANDRÉ, 1880 Malleny Woods, 2 ♀♀, 2 ♂♂, 12.vi.2010, leg. Liston. Two of the females (Malleny, Bavelaw) have red patches laterally on some abdominal terga. Similarly coloured specimens apparently occur throughout the European range of D. gessneri but in the North increasingly dominate. These have often been identified as Dolerus labiosus Konow, 1897 or D. gessneri labiosus by earlier workers. A taxonomic distinction is not justified (Goulet 1986), as was already recognized by Benson (1934). Superficially, apart from its conspicuously larger size, D. gessneri may in Britain most easily be confused with D. yukonensis., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 35, {"references":["Goulet, H. 1986: The genera and species of the Nearctic Dolerini (Symphyta: Tenthredinidae: Selandriinae): classification and phylogeny. - Memoirs of the Entomological Society of Canada 135: 1 - 208.","Benson, R. B. 1934: Additions to the list of British Dolerinae (Hymenoptera, Symphyta). - Entomologist's Monthly Magazine 70: 11 - 13."]}

Pristiphora groenblomi (LINDQVIST, 1952) Ben Vraikie (1150ft), near Moulin, 1 ♂, 8.vi.2010, leg. Halstead. In Britain previously known only from Aviemore (Benson 1958) and Upper Deeside (Liston 1985)., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 49, {"references":["Benson, R. B. 1958: Hymenoptera, Symphyta. - Handbooks for the Identification of British Insects 6 (2 c): 139 - 258.","Liston, A. D. 1985: On some sawflies (Hymenoptera, Symphyta) from Upper Deeside. - Entomologist's Record and Journal of Variation 97: 94 - 95."]}

Claremontia uncta (KLUG, 1816) Fealar Gorge, NN9979, Perths. (89), 1 ♀, 15.v- 9.vi.1999 (1), leg. Bland, det. Liston. Claremontia uncta, together with C. tenuicornis and C. alchemillae, forms a complex of biologically and morphologically poorly understood species (Liston et al. 2006). According to recent determinations, all three are present in Scotland., Published as part of Liston, A. D., Knight, G. T., Heibo, E., Bland, K. P., Barstad, Trond Elling, Blank, S. M., Boeve, J. - L., Fiedler, K., Grearson, K. J., Halstead, A., Jacobs, H. - J., Jansen, E., Lonnve, O., Prous, M., Robinson, J. & Taeger, A., 2012, On Scottish sawflies, with results of the 14 International Sawfly Workshop, in the southern Highlands, 2010 (Hymenoptera, Symphyta), pp. 1-68 in Beiträge Zur Entomologie = Contributions to Entomology 62 on page 34