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Considering the vast importance of peptide and protein interactions with inorganic surfaces, probing hydrogen bonding during their adsorption on metal oxide surfaces is a relevant task that could shed light on the essential features of their interplay. This work is devoted to studying the dipeptides' adsorption on anatase nanoparticles (ANs) in light and heavy water to reveal differences arising upon the change of the major hydrogen bonding carrier. Thermodynamic study of six native dipeptides' adsorption on ANs in both media shows a strong influence of the solvent on the Gibbs free energy and the effect of side-chain mobile protons on the entropy of the process. The adsorption is endothermic irrespective of the medium and is entropy-driven. Computer simulations of peptide adsorption in both media shows similarity in binding via an amino group and demonstrates structural features of protonated and deuterated peptides in obtained complexes. Calculated peptide- anatase nanoparticle (AN) descriptors indicate surface oxygens as points of peptide-nanoparticle contacts.

Bonding properties in the crystal of 4,5-dichloro-l,2,3-dithiazolium chloride (Appel's salt) were studied using a combination of single-crystal high-resolution X-ray diffraction data and the orbital-free quantum crystallography approach. A QTAIM-based topological model shows the proximity of S—C and S—N bonds to the sesquialteral type and establishes the low S—S bond order in the l,2,3-dithiazolium heterocycle. It is found that the electrostatic potential carries the traces of a common positive area on the junction of interatomic zero-flux surfaces of S1 and S2 atomic basins; meanwhile the exchange energy density per particle shows perfectly here two separate minima through which the two bond paths run. Thus, the pair intermolecular interactions Cl−...S1 and Cl−...S2 formed by the common chloride anion placed near the center of the S—S bond are categorized as chalcogen bonds.

Treatment of 4-phenyl-5H-1,2,3-dithiazole-5-thione with iodine in acetonitrile yielded crystalline product with thione-iodonium three-center halogen bond and triiodide anion bound with two iodine molecules by the typical halogen bonds. At the level of a theoretical study of electron density and its gradients, the similarity of electronic properties of the central iodine atom in bridged moiety [S−I−S]+ and in triiodide anion [I−I−I]− has been illustrated. The experimental and theoretical Raman spectra of iodonium salt are discussed: the assignment of the bands corresponding to the iodonium bridged fragment vibrations has been made on the basis of calculated ab initio data.

Ionothermal synthesis of carbon nitride paved the way to a new structural allotrope—polytriazine imide. In this work, we screen available precursors for pristine polytriazine imides and for their graphitic analogs narrowing it to the melamine—urea mixture as the most promising starting material. Photocatalytic activity of materials verified in reaction of benzyl alcohol oxidation to benzaldehyde, which is known to be highly requested chemical with thousands of tons of annual production. Therefore "green" and selective route of production is highly desired. Developed PTI-LiCl was tested for selective photooxidation of benzyl alcohol to benzaldehyde, demonstrating precious conversion and selectivity rates—96.3% and 91.6%, respectively after 5 hours of UV irradiation. Detailed physical-chemical characterization revealed that PTI materials possessed more ordered and highly condensed structure which grant them improved photocatalytic properties in comparison to graphitic carbon nitride polymorph. Graphical abstract represents two different lines of materials which are known to be various polymorphs of carbon nitride studied comparatively in the present work. One of them is convenient graphitized carbon nitride which is prepared from precursors (melamine, urea or thiourea) via the simple thermal treatment. Another line of materials are prepared via thermal treatment in the eutectic mixture of molten salts. The later line of materials is more active in selective photocatalytic oxidation of benzyl alcohol.

The insight into the behavior of polyiodides under non-ambient conditions can enrich the practical applications due to obtaining materials with adjustable and tunable conducting properties. In this work Raman spectroscopy study in the range 0 – 6.5 GPa has been performed for dithiazolylidene-dithiazolium zigzag polyiodide with N-H…N hydrogen bond. Variations of band positions in the low-wavenumber region of Raman spectra have been attributed to the changes in the anionic part of the unit cell. The association of different interacting polyiodide subunits at pressure above 1.5 GPa leads to the emergence of the bands at 98 and 115 cm-1 due to consistent vibrations in the I82- zigzag. The emergence of the band at 159 cm-1 above 0.28 GPa can be assigned to N-H…N hydrogen bond vibration. The obtained results depict undergoing structure transformations: the stronger are cation…cation and anion…anion interactions the more likely is the observation of conducting properties due to the formation of polyiodide zigzag and strongly-bound hydrogen-bonded fragment.

Fundamentals of inorganic-organic interactions are critically important in the discovery and development of novel biointerfaces amenable for utilization in biotechnology and medicine. Recent studies indicate that proteins interact with surfaces through limited adsorption sites. Protein fragments such as amino acids and peptides can be used for interaction modeling between complex biological macromolecules and inorganic surfaces. During the last three decades, many valid and sensitive methods have been developed to measure the physical chemistry fundamentals of those interactions: isothermal titration calorimetry (ITC), surface plasmon resonance (SPR), quartz crystal microbalance (QCM), total internal reflection fluorescence (TIRF), and attenuated total reflectance spectroscopy (ATR). The simplest and most affordable technique for the measurement of adsorption is the depletion method, where the change in sorbate concentration (depletion) after contact with solution-dispersed sorbent is calculated and assumed to be adsorbed. Adsorption isotherms based on depletion data provide all basic physicochemical data. However, adsorption from solutions requires longer equilibration times due to kinetic restrictions and sorbents with a high specific surface area, making it almost inapplicable to macroscopic fixed plane surfaces. Moreover, factors such as the instability of sols, nanoparticle aggregates, sorbent crystallinity, nanoparticle size distribution, pH of the solution, and competition for adsorption, should be considered while studying adsorbing peptides. Depletion data isotherm construction provides comprehensive physical chemistry data for literally every soluble sorbate yet remains the most accessible methodology, as it does not require expensive setups. This article describes a basic protocol for the experimental study of peptide adsorption on inorganic oxide and covers all critical points that affect the process.

For the first time, a simple and sensitive electrochemical sensor based on a screen printed electrode (SPE) modified with titanium dioxide (TiO2) and polytriazine imide submicrostructured composite (TiO2-PTI) has been developed for the simultaneous detection of fipronil (FIP) and its toxic metabolite fipronil sulfone (FIP-S). The submicrostructured composite material based on TiO2 and PTI was obtained by simple hydrothermal treatment of the Ti peroxocomplexes in the presence of pristine. This carbon nitride allotrope has better crystallinity and conductivity than its graphitic analog. It was found that the TiO2-PTI submicrostructured composite enhanced the electrochemical sensing of the SPE electrode towards FIP and its metabolite FIP-S in 0.1 M Britton-Robinson buffer (pH 10) at the oxidation potentials of 0.82 V and 0.94 V, respectively. In addition, it showed good stability and reproducibility for the determination of both analytes. Under optimal conditions, the peak currents by square wave voltammetry were found to vary linearly with FIP and FIP-S concentrations in the range from 0.01 to 10 μM and from 10 to 50 μM, with a detection limit of 8.42 nM, 3.6 μg/kg for FIP and 9.72 nM, 4.04 μg/kg for FIP-S. This sensor was successfully used to detect FIP and FIP-S in eggs and water samples with good recoveries of 90%–106.6%, which was validated by liquid chromatography tandem mass spectrometry.

The affinity of biomolecules, such as peptides and proteins, with inorganic surfaces, is a fundamental topic in biotechnology and bionanotechnology. Amino acids are often used as “model” bits of peptides or proteins for studying their properties in different environments and/or developing functional surfaces. Despite great demand for knowledge about amino acid interactions with metal oxide surfaces, studies on the issue represent a fragmentary picture. In this paper, we describe amino acid adsorption on nanocrystalline anatase systematically at uniform conditions. Analysis of the Gibbs free adsorption energy indicated how the aliphatic, aromatic, polar, and charged side chain groups affect the binding affinity of the amino acids. Thermodynamic features of the L-amino acid adsorption receive thorough interpretation with calculated molecular descriptors. Theoretical modelling shows that amino acids complex with TiO2 nanoparticles as zwitterions via ammonium group., This work was financially supported by the Russian Foundation for Basic Research (grant no. 15-03-07834-a). I.K. acknowledge the financial support from Spanish MINECO (CTQ2014-52956-C3-1-R and MAT2016-78155-C2-1-R).

Important aspects of dye-sensitized solar cells (DSSCs) fabrication based on dyes including benzothiadiazole unit were investigated. Two absorption peaks of the dyes covering the 330–551 nm region and possessing moderate band energy gap (1.83–2.16 eV) were found to be important to demonstrate high photovoltaic efficiency ( η > 8) in metal free iodide/iodine electrolyte composed DSSCs. Furthermore, the dye energy band gap determined from optical spectra decreases with the increase of DSSCs short circuit photocurrent density, which in turn linearly increases the photovoltaic efficiency of DSSCs. While the RedOx potentials of dyes are less functionally related to the photovoltaic properties of the DSSCs, their appropriate values (0.67 ≤ E ox ≤ 1.1 V and −1.75 ≤ E red ≤ −0.91 V) can be important for efficient DSSCs. Fabrication details increasing photovoltaic efficiency of the devices based on dyes with benzothiadiazole unit were found. The relationships obtained in the work can be used for preliminary prognosis whether a newly synthesized dye is a promising metal-free sensitizer for DSSCs or not.

The crystal structure and properties of (Z)-4-chloro-5-((2-((4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino)phenyl)amino)-1,2,3-dithiazol-1-ium oligoiodide (C2/c) synthesized from the initial bis(4-сhloro-5H-1,2,3-dithiazolo-5-ylidene)benzene-1,2-diamine (P21/c) have been characterized by various experimental and theoretic methods. The superposition of atomic basin boundaries in the electron density and in the electrostatic potential does not confirm the halogen bonding between the triiodide anion and sulfur atoms in cation. On the other hand, in the studied oligoiodide, the charge-assisted iodine–iodine halogen bonds are observed between the strongly asymmetric triiodide and diiodine units; thus, the oligoiodide anion includes at least two diiodine fragments with bond lengths 2.7334(4) and 2.7786(5) A bound. This key trait has resulted in characteristic spectral and thermal features. Raman spectra do not contain typical triiodide bands but only those that are expectable for bound diiodine at 157 and 179 cm−1. Thermal decomposition has demonstrated release of both diiodine molecules within one decomposition stage without melting.

O.I. Bol’shakov1, bolshakovoi@susu.ru V.A. Potemkin1, potemkinva@susu.ru M.A. Grishina1, grishinama@susu.ru A.S. Galushko2, galas74@inbox.ru S.V. Merzlov1, bostonbruins.2011.6@gmail.com R.S. Morozov1, yanatulskoi@mail.ru A.O. Shchelokov1, artyom.shchelokov@yandex.ru V.V. Popov3, Popov.ioc@gmail.com 1 South Ural State University, Chelyabinsk, Russian Federation 2 Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow, Russian Federation 3 Wayne State University, Detroit, MI, USA Большаков Олег Игоревич – кандидат химических наук, научный сотрудник Управления научной и инновационной деятельности, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: bolshakovoi@susu.ru Потемкин Владимир Александрович – научный сотрудник Управления научной и инновационной деятельности, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: potemkinva@susu.ru Гришина Мария Александровна – главный научный сотрудник Высшей медико- биологической школы, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: grishinama@susu.ru Галушко Алексей Сергеевич – аспирант лаборатории металлокомплексных и наноразмерных катализаторов (№ 30), Институт органической химии им. Н.Д. Зелинского, РАН. 119991, г. Москва, Ленинский пр. 47. E-mail: galas74@inbox.ru Мерзлов Сергей Владимирович – инженер кафедры экологии и природопользования, химический факультет, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: bostonbruins.2001.6@gmail.com Морозов Роман Сергеевич – аспирант кафедры экологии и природопользования, Южно- Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: yanatulskoi@mail.ru Щелоков Артем Олегович – студент кафедры химической технологии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: artyom.shchelokov@yandex.ru Попов Вадим Владимирович – постдокторант факультета биомедицинской инженерии, Университет Уэйна, Wayne State University, 42. W. Warren Ave. Detroit, MI 48202, MI, USA. E-mail: popov.ioc@gmail.com Affinity characteristics of biomolecules, such as peptides and proteins, towards inorganic surfaces in general and to titanium oxide in particular become crucial in biotechnology and bionanotechnology. Amino acids are often used as “model” bits of peptides or proteins for studying their properties in different environments, and/or developing functional surfaces. Despite the great demand for knowledge about amino acid interactions with metal oxide surface, studies on the issue lack in consistency and represent a fragmentary picture. This paper is an attempt to study amino acid adsorption on nanocrystalline anatase systematically at uniform conditions. Features of the L-alanine adsorption have been revealed and interpreted with quantum-chemical calculations. Особенности взаимодействия биомолекул, таких как протеины и пептиды с неорганическими поверхностями вообще и с оксидом титана в частности становятся ключевым фактором биотехнологии и бионанотехнологии. Аминокислоты часто используются в качестве модельных фрагментов пептидов и протеинов для изучения их свойств в различных средах и при изучении новых поверхностей. Несмотря на высокий запрос на фундаментальные представления о взаимодействии биомолекул с поверхностью оксида титана, знания в этой области представлены фрагментарно и не дают целостной картины. В этой статье проведена попытка изучения сорбции аминокислот на оксиде титана в унифицированных условиях. Сорбция L-аланина была интерпретирована квантово- механическим моделированием. The reported study was funded by RFBR according to the research project № 15-03-07834-a.

Surface properties of the nanostructured materials are essential in attaining particular functionality, which is why there are a plethora of surface modification methods applied during or past the synthesis of nanoparticular substrates. Depending on the resulting content of the surface it could be heterophase forming modifications or pristine titania modifications. In this communication, we study a novel approach to pristine titania surface alteration by controlled chemisorption of the stable water-soluble titanium complex on the nanocrystalline anatase. Following on-air calcination for removal of organic residues converts chemisorbed complexes into oxide phase increments. Such an approach retains crystallinity and specific surface with simultaneous withdrawal of surface hydroxyl groups.

Composite microporous SiO2-TiO2 spheres and micro/mesoporous TiO2 spheres were prepared via the template-free two-step synthetic route using aqueous peroxotitanate solution and tetraethyl orthosilicate (TEOS) as precursors. Both the composite SiO2-TiO2 and pure TiO2 spheres prepared by the solvent-exchange method were initially non-porous, but the applied reflux treatment in water-ethanol suspension successfully transformed them into microporous materials with high apparent surface areas approaching 500 m2·g− 1 and the micropore volume of 0.17 cm3·g− 1, while maintaining the same morphology. The prepared composites retained high values of pore volume and specific surface area up to 400 °C of thermal treatment temperature. The crystallization of TiO2 into the anatase phase in the mixed oxide occurred only at 700 °C, that process was also accompanied by the significant reduction of pore volume, as well as apparent surface area values. The prepared materials were tested as adsorbents for the lead(II) removal; they demonstrated high adsorption capacities, reaching 340 mg(Pb2 +)·g− 1. Moreover, the mixed silica-titania oxide was found to be more efficient adsorbent at low pH values., South Ural State University is grateful forfinancial support of theMinistry of Education and Science of the Russian Federation (grant No16.2674.2014/K). University of Oviedo gratefully acknowledgesfi-nancial support from the Spanish MINECO (MAT2013-40950-R andMAT2016-78155-C2-1-R). Igor Krivtsov thanks for the support theRussian Foundation for Basic Research 16-29-10757-ofi.

Analysis of iodine-derived chalcogenazolo(ino)quinolinium mono- and triiodides shows that the covalently bonded iodine atoms in the fragments C(sp2)–I and C(sp3)–I differ significantly in iodide–iodine halogen bonding ability. The local and integrated characteristics of kinetic, potential, and total electronic energy for C–I covalent bond have been examined. It has been found that both delocalization indices of iodine covalent bond and the total electronic energy density integrated over carbon–iodine interatomic surface can be used as quantitative criteria of iodine-derived cation ability to form the halogen bond with triiodide anion in crystals.

Reaction of 1-arylethanone oximes with S 2 Cl 2 gives 4-aryl-5-chloro-1,2,3-dithiazol-1-ium chlorides, whose in situ treatment with copper powder affords 4,4’-diaryl-5,5’-bi-1,2,3-dithiazoles.

S-Acyl cysteine peptides containing alpha-, beta- or gamma-amino acid residues undergo long-range S- to N-acyl transfer to give analogs of native tripeptides and tetrapeptides containing additional carbon atoms in the chain. The ease of intramolecular S -> N-acyl transfer relative to intermolecular transacylation is favored increasingly for 9?12?

A synthesis of 17α-ethynylestradiol-labeled native peptides is reported. The peptide moiety is tethered to the steroid hormone by a 1,2,3-triazole bridge formed by a CuAAC reaction in which the azido group of the peptide combines with the terminal acetylenic moiety of ethynylestradiol to link the two bioactive molecules. Thus bioconjugates containing the hormone moiety at three positions within the peptide molecule could be useful targets for hormono–enzyme interaction studies.

The treatment of 5H-1,2,3-dithiazole-5-thiones 1 in chloroform under reflux and 5H-1,2,3-dithiazol-5-ones 2 in THF at room temperature with primary aliphatic amines and benzylamine afforded 1,2,5-thiadiazole-3(2H)-thiones 3 and 1,2,5-thiadiazol-3(2H)-ones 6, respectively. The structure of dithiazolone 3f was confirmed by X-ray diffraction analysis. The reaction of dithiazolone 2e bearing an electron-donating methyl group in the 4-position gave 2-oxoacetamide 7e in high yield. The reaction of thiones 1 with secondary aliphatic amines in DMSO yielded 2-iminothioacetamides 8 in moderate yields together with elemental sulfur. Interestingly, the treatment of dithiazolones 2 with secondary amines under the same conditions afforded 2-oxoacetamides 9—the products of the hydrolysis of corresponding imino derivatives 10, which was isolated as 10b. A general mechanism was proposed for the formation of the products.

Substituted ethanone oximes react with S2Cl2 and pyridine to give 1,2,3-dithiazolium chlorides. The treatment of these products with malonodinitrile in dichloromethane affords 4-substituted 5 H-1,2,3-dithiazol-5-ylidenes. The reaction of the latter compounds with n-butylamine unexpectedly yielded addition products at one of the nitrile groups, viz. substituted 1,2,3-dithiazol-5-ylideneethanimidamides.

Complete eradication of HIV-1 infection is impeded by the existence of latent HIV-1 reservoirs in which the integrated HIV-1 provirus is transcriptionally inactive. Activation of HIV-1 transcription requires the viral Tat protein and host cell factors, including protein phosphatase-1 (PP1). We previously developed a library of small compounds that targeted PP1 and identified a compound, SMAPP1, which induced HIV-1 transcription. However, this compound has a limited bioavailability in vivo and may not be able to reach HIV-1-infected cells and induce HIV-1 transcription in patients. We packaged SMAPP1 in polymeric polyethylene glycol polymethyl methacrylate nanoparticles and analyzed its release and the effect on HIV-1 transcription in a cell culture. SMAPP1 was efficiently packaged in the nanoparticles and released during a 120-hr period. Treatment of the HIV-1-infected cells with the SMAPP1-loaded nanoparticles induced HIV-1 transcription. Thus, nanoparticles loaded with HIV-1-targeting compounds might be useful for future anti-HIV-1 therapeutics.

This review aims at delivering an overview of the synthetic utility of benzotriazole and its derivatives for the preparation of oxygen-containing heterocycles. This review serves both as a synthetic guide and as a theoretical handbook of benzotriazole-assisted preparations of oxygen heterocycles and offers a complete overview of existing applications for benzotriazole and its derivatives in heterocyclic synthesis. Multiple examples reveal the superiority of benzotriazole-based approaches over conventional ones.

The study concerns molecular design and theoretical study of novel prospective organic sensitizers based on D–A–π–A concept. A modification of the concept (DA–π–A) and new ways for design of organic sensitizers are proposed. The study shows thatπ-block plays a key role for the wavelength shift in UV-Vis spectra. An existence of element of higher periods in theπ-block provides a noticeable bathochromic shift. The thienyl bridge in A-block provides a red shift with respect to phenyl bridge for[1,2,5]oxadiazolo[3,4-c]pyridines while the phenyl bridge provides a red shift with respect to thienyl bridge for[1,2,5]selenadiazolo[3,4-c]pyridines. The maximal wavelengths are observed for DA-blocks with aliphatic/alicyclic fragments we proposed. An influence of enthalpy of formation and polarity of DA-blocks on bathochromic shift is shown. The quantitative dependencies of wavelengths on the enthalpies and dipole moments are determined. The maximal oscillator strengths are observed for the planar DA-block. Therefore, the conditions for design of compounds possessing the maximal wavelengths and oscillator strengths are different: the latter presupposes the planar structure of DA-block while the first presupposes an existence of nonplanar aliphatic/alicyclic fragments. Thus, the further design of organic sensitizers should include some combination of these concepts.

Development of biologically active polymers is an active area of research due to their applications in varied and diverse fields of biomedical research: cell adhesion, tissue proliferation, and drug delivery. Recent advances in chemical modification allow fine-tuning of the properties of biomedical polymers to improve their applications: blood circulation half-life, stimuli-responsive degradation, site-specific targeting, drug loading, etc. In this article, convergent synthesis of polymerizable macromonomers bearing a site-specific ligand (RGD peptide) using a low molecular weight MA-poly(ethylene glycols) (PEGs) is presented. The method affords macromonomers useful as the starting materials to produce biomedical polymers. We found matrix assisted laser desorption/ionization mass spectromerty convenient in monitoring the conjugation process via step-by-step following of PEG modification.

(no carbonsignals in the region 160–220 ppm).Careful investigation of this reaction showed that the bestyield was achieved when 5-fold excess of sodium ethoxide wasused (55% yield). Note that this amount significantly exceededthe required quantity of the reagent (one or two equivalents).However, when less amount of the reagent was used, some ofthe starting thione

Reaction of 1-arylethanone oximes with S 2 Cl 2 gives 4-aryl-5-chloro-1,2,3-dithiazol-1-ium chlorides, whose in situ treatment with copper powder affords 4,4’-diaryl-5,5’-bi-1,2,3-dithiazoles.

Chemical ligation via O- to N-acyl transfer of O-acylated serine containing peptides affords serine containing native peptides via 8- and 11-membered cyclic transition states opening the door to a wide variety of potential applications to peptide elaboration. The feasibility of these traceless chemical ligations is feasible as supported by computation.

The azide allows convenient and effective access to various diazo compounds and a number of azides including α-azido acids, esters, thioesters, amides, and peptides.

Reaction of aryl-substituted dithiazolethiones (I) and -ones (VI) with primary amines proceeds with recyclization to give thiadiazolethiones (III) and -ones (VII), respectively.

We here report the synthesis and biological evaluation of rare 4-substituted-5-phenylimino, 5-thieno- and 5-oxo-1,2,3-dithiazoles. Dithiazoles were selectively obtained in moderate to high yields (25–73%) via a one-pot reaction from various ethanoneoximes with sulfur monochloride, pyridine in acetonitrile followed by treatment by corresponding nucleophiles (aniline, thioacetamide and formic acid). All the synthesized compounds were screened for their antibacterial (against bacteria Escherichia coli, Salmonella enterica serovar Typhimurium, Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Bacillus cereus and Listeria inocua), antifungal (against pathogenic strains Candida albicans, Candida glabrata, Candida tropicalis and Issatchenkia orientalis) and antitumor (on human cell lines MCF-7 and MDA-MB-231) activity. 4-(2-Pyridinyl)-5H-1,2,3-dithiazole-5-thione and 4-ethylcarboxyl-5H-1,2,3-dithiazole-5-thione (5d, 5h) that are active against Gram-positive bacteria are significantly active against fungi. 4-(2-Benzofuranyl)-5-phenylimino-5H-1,2,3-dithiazole (4e) exerts antiproliferative activity.