However, scalable methodscapable of depositing MoS2 at low temperatures are scarce.Herein, we present a toolbox of advanced plasma-enhanced atomic layerdeposition (ALD) processes, producing wafer-scale polycrystallineMoS2 films of accurately controlled thickness. Our ALDprocesses are based on two individually controlled plasma exposures,one optimized for deposition and the other for modification. In thisway, film properties can be tailored toward different applicationsat a very low deposition temperature of 150 °C. For the modificationstep, either H2 or Ar plasma can be used to combat excesssulfur incorporation and crystallize the films. Using H2 plasma, a higher degree of crystallinity compared with other reportedlow-temperature processes is achieved. Applying H2 plasmasteps periodically instead of every ALD cycle allows for control ofthe morphology and enables deposition of smooth, polycrystalline MoS2 films. Using an Ar plasma instead, more disordered MoS2 films are deposited, which show promise for the electrochemicalhydrogen evolution reaction. For electronics, our processes enablecontrol of the carrier density from 6 × 1016 to 2× 1021 cm–3 with Hall mobilitiesup to 0.3 cm2 V–1 s–1. The process toolbox forms a basis for rational design of low-temperaturetransition metal dichalcogenide deposition processes compatible witha range of substrates and applications.Two-dimensional MoS Besides stability as single, subnanometerthick monolayers, their extraordinary electronic, optical, mechanical,and chemical properties give TMDCs great potential in a range of applicationsincluding (opto)electronics, energy storage, and catalysis.5 Some 30 different 2D TMDC materials are known that share the compositionMX2, where M is a transition metal or Sn and X is S, Se,or Te. The majority of studies have focused on semiconducting TMDCs,such as MoS2 and WS2, which are among the mostpromising alternatives to silicon for future nano(opto)electronics.9 The flexible nature of 2D materials also makes them promising forflexible devices including displays and various sensors.11 TMDCs have also been intensively studied for the electrocatalytichydrogen evolution reaction, a key process in the production of cleanhydrogen, where it promises an affordable and sustainable alternativeto currently used, scarce Pt.16 Hydrogen is expected to play a major role in the carbon-neutralfuture, offering a clean, highly efficient fuel, means for grid stabilization,as well as a green alternative for carbon in steel production, forexample.17Two-dimensional (2D) materialsrank high among the most scientificallyand technologically interesting materials of the early 21st century.Among them, the large family of transition metal dichalcogenides (TMDCs)that includes semiconductors, (semi)metals, and even superconductors18 In general, continuous, high-quality filmswith a controlled and uniform thickness over large, sometimes 3D structuredsubstrates are called for. Many substrates and process flows alsoplace limitations on the applicable thermal budget. Initially, 2Dmonolayers were produced by mechanical exfoliation of bulk crystals.19 Although this method remains in use in researchfor its simplicity and ability to produce high-quality flakes, itcannot be scaled up for production. Chemical vapor deposition (CVD)has emerged as a widespread method for the preparation of high-qualityTMDC flakes and films. Its most common variant utilizing chalcogenideand metal oxide powder precursors22 struggles with thickness control and uniformity and requires hightemperatures from 600 to 1000 °C. Use of metalorganic and halidemetal precursors and gaseous chalcogenide sources improves scalabilityand enables a decrease of the deposition temperature to 400–550°C,25 in favorable cases even 200–300 °C.27 These processes are compatible with back-end-of-line semiconductorprocessing (Tmax ≈ 400–500°C),28 but cannot be applied on typicalplastics and other sensitive materials used in the emerging fieldof flexible electronics (Tmax ≈100–200 °C). Low processing temperatures also simplifydeposition equipment design and require less energy input, which isattractive from both economic and environmental points of view.One of the major factorshindering applications of TMDCs in nanoelectronics,electrocatalysis, and other fields alike is the lack of scalable fabricationmethods.30 Recently, ALD has been increasinglystudied for deposition of TMDCs for a variety of applications.32 ALD processes operate at relatively low temperatures, generallybelow 500 °C. This is particularly true for its plasma enhancedvariant (PEALD) that takes advantage of highly reactive radicals andlow-energy ions.35 PEALD processes depositing semiconductors MoS2 and WS2 at 300–450 °C have been developedin our group,37 while metallic TiS2 films could be deposited even at 150 °C.38Atomic layer deposition (ALD) is an advanced, surface-controlledvariant of CVD that boasts excellent uniformity on large areas andcomplex shapes, accurate thickness control, and high reproducibilityand scalability.39 The deposition of stoichiometric and crystalline MoS2, TiS2, and WS2 films was achieved by additionof sufficient hydrogen to the H2S plasma feed gas, whichprevents excess S incorporation from otherwise happening at theselow temperatures. However, tailoring the chemistry of a single plasmastep in such a manner offers limited control over film properties,as the plasma species play multiple simultaneous roles including removalof ligands of the metal precursor, deposition of sulfur, and supplyingenergy in the form of low-energy ions and other reactive species forcreation and healing of defects.Recently, we showed that tailoring the plasma depositionchemistryenables a decrease of deposition temperature of both semiconductingand metallic TMDCs to record low 100 °C.2 and Ar plasma steps that deposit uniform, crystallineMoS2 films of accurately controlled thickness at a verylow temperature of 150 °C. We discuss the growth mechanisms aswell as effect of plasma conditions for each process. Compared toearlier (PE)ALD processes, the new processes exhibit complementaryand in many cases improved properties as shown by systematic use ofa broad range of microscopy, structural, compositional, and electricalcharacterization techniques. For electronics, carrier densities canbe decreased by 3–5 orders of magnitude, and Hall mobilitiesincreased by an order of magnitude compared to our earlier low-temperatureprocess. For electrocatalytic HER, the catalytic activity can be tailoredvia changes in the film morphology and crystallinity using the processtoolbox developed in this work.In this study, we show thatimproved control over film growth andresulting properties can be achieved by using two separate and individuallyoptimized plasma steps. While the first plasma step removes ligandsof the metal precursor and supplies sulfur, the second step can befurther tailored to control stoichiometry, crystallinity, and electricalproperties, among others. We have developed three processes utilizingH22.1tBu)2(NMe2)2, which reacts on the substratesurface in self-limiting manner. Then, excess unreacted precursorand byproducts are purged away with the help of Ar gas. The followingB step consists of exposure to a plasma, here a mixed H2S/H2/Ar plasma, which removes the ligands of the adsorbedMo precursor and supplies S, again in a self-limiting manner. A secondpurge completes an “AB” ALD cycle, which can then berepeated until the target thickness is reached. In such an AB cycle,the plasma conditions of the B step can be varied to tailor film growthand properties. An example of this from our earlier work is shown 2 flow ratio  leadto rough morphology  results in lower roughness and H impurities, but alsopoorer crystallinity and electrical properties.39 These examples illustrate limitations of the AB approach.x films. The first plasma step (B step) is optimized for deposition, namely, removing ligands of the adsorbed metalprecursor and sulfur deposition. Here, we typically use a low H2 flow ratio in the B step (B0.20) to limit H incorporationinto the films. The second plasma step (C step) is then used for modification, that is, removal of excess S (if present),modifying crystallinity, and tuning film properties. The plasma feedgas in this step is denoted as a subscript of C . Thus, we refer to our process with an Ar plasma modification step,for example, as the A B0.20 CAr process.In this contribution, we explore the ample opportunities that PEALDoffers for tailoring TMDC film growth and properties via rationalprocess design and control of process conditions. A typical PEALDprocess illustrated in ow ratio 1 from 0.rphology 1c. Usinghis work 1b, we us2, Ar, H2/Ar, and H2S/Ar), (2) modifying plasma conditions , and (3) changing thefrequency or periodicity of the C step, i.e., only applying it every n ALD cycles (denoted n(A Bx) Cy). Furthermore, eachC step can be combined with different plasma compositions and parametersin the B step, different deposition temperatures, and so forth, givingrise to near infinite possibilities as well as conditions to investigate.We have used three different approaches to controlthe C step:(1) using different plasma gases  or every10 cycles (10(A B0.20) CH2)) or an Ar plasmastep in each cycle (A B0.20 CAr) to remove theexcess S and crystallize the films. A schematic of the ALD processesis shown in Figure S1 (Supporting Information). Throughout the manuscript, we discuss processes depositing MoS2 at a fixed temperature of 150 °C. The concepts are regardlessapplicable to other low temperatures, as we show for the A B0.20 CH2 process, as well as other TMDCs.Figure S2 in the Supporting Information) and result in excellent waferscale uniformity .These ABCprocesses allow for submonolayer level thickness controlby simply changing the number of ALD cycles . In 2 films as HER catalysts.In ormation S5. In Seormation S5. In Se2.22.2.12 plasmain a C step builds on our earlier finding of hydrogen preventing excesssulfur incorporation, which otherwise occurs during low-temperaturePEALD of TMDCs.39 Using H2Splasma with a low H2 flow ratio such as 0.20 yields a-MoS3.5 films at 150 °C. In contrast, the A B0.20 CH2 process results in crystalline c-MoS1.9 films at 150 °C as shown by the characteristic E12g and A1g Raman modes of MoS2 andstoichiometries determined by XPS  increased from 0.65 to 1.0–1.2 Å. Theprocess showed self-limiting characteristics as expected for ALD interms of the GPC, S/Mo ratio, resistivity, and Raman intensity (Section S2.1 in the Supporting Information).A 20 s H2 plasma exposure was deemed saturating and waschosen for further experiments. Besides the temperature of 150 °Cdiscussed here, we found that the process deposited crystalline MoS2 films at temperatures ranging from 100 to 250 °C (Section S2.2 in the Supporting Information).The idea of using Hd by XPS 2. This s2 gas instead of H2 plasma had noeffect on the stoichiometry or crystallinity of a-MoS3.5, showing that plasma-generated species such as radicals and ionsare essential to the process (Table S1).Using H2 plasma, the crystallinity was observed to decreasewhen pressure was increased ;thus, the lowest pressure allowing for reliable striking of H2 plasma (20 mTorr) was used in further experiments. The pressuredependence suggests that while H radicals likely play a major rolein changing stoichiometry from MoS3.5 to MoS1.9, low-energy ions, such as H3+,40 may have a beneficial effect on crystallinity.41Using H0.20 process are smooth CH2, may lead to smoother film morphology. The A B0.20 cycles deposit a-MoSx2+, whichlacks the anisotropy of 2D MoS2, and may therefore hinderfin growth (n(A B0.20) CH2 process to result in c-MoS2 films, periodic H2 plasma exposures must be able to remove excess S and crystallizethe deposited material as MoS2 over the thickness of severalÅ deposited during n A B0.20 cycles.Raman spectroscopy and XPS suggest that this is indeed the case, asapplication of H2 plasma every 3, 5, 10, or even 20 A B0.20 cycles resulted in crystalline films with MoS1.9 composition . Thisis expected, considering that more than 40% of the S atoms depositedby the n A B0.20 cycles are removed whenthe H2 plasma step converts a-MoS3.5 to c-MoS1.9.Further insights into growth mechanisms were soughtfrom 0.20 cycle followinga H2 plasma C step was between 1.5 and 2.5 Å, whichis much higher than the steady-state GPC of the A B0.20 process (0.7 Å). For n > 1, the GPC quicklydecreased in the following A B0.20 cycles, such that theaforementioned steady-state GPC was reached after 5–10 AB cycles.This is in line with a transition from a c-MoS2 surfaceto an a-MoSx2+ surface when multiple AB0.20 cycles are applied (x2+ ishypothesized to contain a lower density of reactive sites where theMo(NtBu)2(NMe2)2 precursorcan adsorb, which explains the decrease in GPC despite the increasein S/Mo stoichiometry compared to c-MoS2.39 XPS measurements confirmed that A B0.20 cyclesindeed deposit MoSx2+ on a c-MoS2 surface (Section S2.3 in the Supporting Information).The apparent GPC in the first A B applied 3d. a-MoSn. The roughness of the films deposited using the A B0.20 CH2 process was high, with features as highas 10 nm observed for a nominally 7 nm thick film  data on the arealdensity of atoms deposited allows us to estimate that on average,∼100 Ar+ ions with a mean kinetic energy of 25–30eV are needed to remove a single S atom at the optimized 60 s Ar plasmaexposure (Section S2.6 in the Supporting Information).For an Ar plasma at 1 mTorr, we can estimate basedon earlier measurementsin a similar reactor48 to increase the energy of Ar+ ions and decrease the amount of required ions and processingtime.Already a 10 s exposure at 30 V substrate bias (estimated mean ionenergy of 45–55 eV) resulted in efficient S removal (Section S2.5 in the Supporting Information). However, the crystallinity as inferred from the intensity andwidth of the MoS2 Raman modes remained low within the rangeof plasma exposures (10 to 60 s) and biasing voltages explored (30to 60 V). We explored the use of RF substrate biasing removal 5a and si48 Lin et al.49 found the damage thresholdof Ar+ ions for a MoS2 monolayer to be between25 and 35 eV. Lu et al.50 used 50 eV Ar+ ions to selectively remove the top S layer of bulk MoS2. Molecular dynamics simulations52 have suggested Ar+ ion sputtering thresholds of approximately20 and 50 eV for S and Mo atoms in a MoS2 monolayer. Ourexperiments suggest that there is also a lower energy threshold belowwhich Ar+ ions are ineffective in removing excess S. Plasmasources producing a high ion flux but low ion energies53 and tailored waveform biasing45 thatcan achieve accurate ion energy control are likely to be useful toolsfor the A B0.20 CAr and related processes.The detrimental effect of substrate biasing is likelydue to ionenergies exceeding a material dependent damage threshold.2.32.3.10.20 CH2, 10(A B0.20) CH2, and A B0.20 CAr processesoptimized, we proceeded to compare these to each other along witha more detailed characterization of the crystallinity, morphology,impurities, and electrical properties. In addition to these threeABC processes developed in this work, we have included data for ourpreviously developed A B0.80 process,39 which also deposits crystalline films at the same temperatureof 150 °C. A table comparing the properties of the three ABCprocesses to each other as well as to different AB processes  is providedin the Supporting Information (Section S3.4). This comparison highlights the improved control of the ABC approach,which significantly expands the range of film properties achievedcompared with the preceding AB processes. Section S3.5 compares our processes and film characteristics to thosein the literature. Finally, besides the selected three, other evaluatedABC processes including different plasma steps  added to the A B0.80 process aredescribed in the Supporting Information (Section S5).With the A B12g and the out-of-plane A1g MoS2 modes revealedclear differences between the processes , while the peaks broadenwith increasing defectivity.54 For filmsof similar thickness, we have also observed a correlation of increasedRaman intensity with improved crystallinity. Disorder-activated LO(M),TO(M), and ZO(M) modes provide another signature of defectivity, asthe intensity ratio of these modes to E12g and/orA1g increases with increasing defect density.54 All of these metrics suggest that the best crystallinequality was obtained using the A B0.20 CH2 process,which is also clearly improved over the A B0.80 process.The E12g fwhm of the A B0.20 CH2 process is comparable to or even lower compared to MoS2 deposited using other methods at 300–500 °C . ApplyingH2 plasma only every 10 cycles  CH2 process) resulted in clearly higher defectivitycompared to that of the A B0.20 CH2 process.The A B0.20 CAr plasma process yielded fwhm’sbetween the two H2 plasma based processes but much lowerpeak intensities, which may be due to its smaller crystallite sizediscussed below.For a fair comparison of crystallinity, 5 nm thickfilms were deposited by using each of the processes. Deconvolutionof Raman spectra in the region of the in-plane Erocesses 6a. The w2 basal planes was observed for all of the processesat a similar position, slightly below that of a bulk reference. Onlythe A B0.80 process showed a clear shift to smaller angles,which suggested a larger spacing between the basal planes. This maybe due to the large amount of hydrogen (∼20 at. %) incorporated.39Complementary information on crystallinity wasobtained using X-raydiffraction (XRD) in symmetric θ-2θ geometry 6b which 0.20 CH2 process,followed by the 10(A B0.20) CH2 and A B0.80 processes. The peak intensity for the A B0.20 CAr process was very low. The width of the peak was thenarrowest for the 10(A B0.20) CH2 process (fwhm= 1.4°); otherwise, it increased in the order of decreasing intensity.As peak broadening is caused by limited crystal size in the directionperpendicular to the substrate, which cannot exceed film thickness,the narrowest peak produced by the 10(A B0.20) CH2 process may be due to its smooth surface and underestimation ofthickness by SE as discussed below with the TEM images.The intensity of the (0002) reflection,which can be taken as ameasure of crystalline order ,was the highest for the A BFigures S22–S24). The images show thatfor the A B0.20 CH2 process, the basal planesof the majority of the MoS2 crystallites were orientedapproximately parallel to the substrate , in good agreementwith SE thickness (4.6 nm). In addition, some fins oriented at randomangles were observed as is common for (PE)ALD TMDCs.56 The film grown by using the 10(A B0.20) CH2 process appeared more disordered, which may be due to its smallercrystallite size or a larger spread in the crystallite orientation CH2 process prevents fins more efficiently than theA B0.20 CAr process. The TEM thickness of 4.6± 0.8 nm, agrees well with SE (4.8 nm). Thus, the SE models andextracted optical constants appear adequate for the A B0.20 CH2 and A B0.20 CAr processes , whereas for the 10(A B0.20) CH2 process, we were unable to develop an accurate modeleven with the TEM thickness information.Cross-sectionaltransmission electron microscopy (TEM) was usedto complement Raman and XRD for crystallinity analysis  CH2, and A B0.20 CAr processes(2 films deposited by ALD and CVD at 200–400°C (Table S10). The crystallite orientationwas quantified from the TEM images, confirming the lowest orientationspread with respect to the substrate surface for the A B0.20 CH2 process followed by the 10(A B0.20) CH2 and A B0.20 CAr processes .The lateral grain size was estimated by manuallyidentifying crystallitesfrom the TEM images, yielding 17 ± 5, 11 ± 5, and 6 ±2 nm for the A Brocesses7. Althou2 plasma based processes is clear: the A B0.20 CH2 process produces the roughest films out of all the studied processes,while the 10(A B0.20) CH2 process produces thesmoothest films.The morphology of the filmsdeposited by using different processeswas further studied by AFM. Figure S26 for images). For the A B0.20 CH2 process, fins begin to form and grow already during the first cycles, resulting in a rapid and continuousincrease of roughness with increasing thickness. In stark contrast,for the 10(A B0.20) CH2 process, surface roughnessis independent of film thickness, showing that this process allowsdeposition of smooth (Rq ≈ 0.5nm) films up to a thickness of at least 7 nm. The films depositedusing the A B0.20 CAr process reach a moderateroughness (Rq ≈ 1.0 nm) with clearlyvisible surface features already at a thickness of 3 nm. However,increasing the thickness beyond 10 nm does not increase the roughnessappreciably, despite an apparent lateral growth of the surface features.Thus, although comparable to the A B0.80 process at a thicknessof ≤7 nm, at higher thicknesses the A B0.20 CAr process produces smoother films. Linking this result tothe TEM images suggests that fins form for the Ar plasma based process,but they do not easily grow as they do for the A B0.20 CH2 and A B0.80 processes .The S/Mo stoichiometryand chemical environment of Mo and S were analyzed by using core-levelX-ray photoelectron spectra. As discussed in detail with the optimizationof each process, the H0.20 CH2 process as an example, the Mo 3d region mainly consistedof a doublet attributed to Mo4+ in MoS2 witha Mo 3d5/2 binding energy (BE) of 229.6 eV (Table S7 in the Supporting Information for more details ofthe peak deconvolution). Minor doublets attributed to Mo5+ and Mo6+ species at Mo 3d5/2 BEs of 231.5and 232.9 eV are likely a result of oxidation of the films in air.59 The observed BEs agree well with average literature values of 229.3± 0.5 eV for MoS2 and 232.7 ± 0.3 eV for MoO3.60 The Mo 3d region was very similarfor all of the ALD processes.Using the A B2– in MoS2 (BE= 226.8 eV). For the A B0.20 CAr process, aminor additional contribution at approximately 228 eV was observed.The S 2p region was analyzed for further information about the S speciespresent .60 The measured S 2p spectrum was practically identical for the A B0.20 CH2, 10(A B0.20) CH2,and A B0.80 processes, which also share a similar stoichiometry.For the more sulfur rich MoS2.3 films deposited using theA B0.20 CAr process, a low intensity doubletat a higher BE (163.4 eV for S 2p3/2) was observed, whichis attributed mainly to the S22– speciespresent in sulfur-rich amorphous MoSx2+. Amorphous MoSx2+ contains sulfur inmany different bonding environments with partially overlapping BEsas discussed in the literature,62 making unambiguousassignment to different S species challenging.S 2s region overlaps with Mo 3d, and can be describedwith onesinglet attributed to Spresent 9b.For t0.20 and A B0.80 processes are shown for reference along with the analyzedA B0.20 CH2 and A B0.20 CAr process. Although the 10(A B0.20) CH2 processwas not analyzed, we expect it to result in a composition resemblingthe A B0.20 CH2 process.The film stoichiometrywas confirmed by Rutherford backscatteringspectrometry (RBS) measurements, which were in good agreement withthe XPS 1.RBS to0.20 step, 0.8–1.4at. %, while clearly more oxygen was detected for the A B0.80 process (6 at. %). As O may result from postdeposition oxidationin air or residual impurities in the ALD reactor, this suggests higherresistance to oxidation for the films deposited using the ABC processes,which may be linked to their lower H concentration. Up to 22 at. %H was incorporated using high H2 flow ratios in B step(A B0.80). The processes based on a B0.20 stepincorporated less H. Approximately 6 at. % of H was found in the amorphoussulfur rich films deposited by the A B0.20 process, whichincreased modestly to 9 at. % when a H2 plasma C step wasadded (A B0.20 CH2). Using an Ar plasma C stepinstead (A B0.20 CAr) decreased the H contentto as little as 2.3 at. %. As our previous work identified H as adopant, decreasing the H content in the films gives promise for bettersemiconductor properties, namely, lower carrier densities and highermobilities.The nitrogen content from incorporated precursor ligandswas lowfor all processes, 0.5–1.4 at. %. Oxygen was observed in lowconcentrations for the processes using a B2.3.30.80 process,which yields the best electrical performance out of low-temperature(<200 °C) AB processes.39 The ABCprocesses resulted in considerably higher four-point-probe (FPP) resistivitiescompared to the A B0.80 process (∼0.3 Ω cm),ranging from approximately 10 Ω cm for both of the H2 plasma processes to ∼200 Ω cm for the A B0.20 CAr process. These resistivity values were reached forfilms at least 5–7 nm in thickness. Thinner films exhibitedhigher resistivities, likely due to increased scattering of chargecarriers at the interfaces as well as at grain boundaries .Motivatedby the decrease of the H content in the films prepared by the newlydeveloped ABC processes, we investigated their electrical propertiesand compared them to the previously developed A B2 plasma based processeswere found to be 3 orders of magnitude lower compared to the A B0.80 process, i.e., in the range of ∼1–3 ×1018 cm–3 (see Section S3.3 in the Supporting Information for detailed results andfurther discussion). Using the A B0.20 CAr process,a further decrease in carrier density to ∼6 × 1016 cm–3 was achieved. The carrier densitiesdecrease with decreasing hydrogen concentration, in line with hydrogenbeing a dopant in the films.39 The relationshipis not linear, however, suggesting that other factors including chemicalbonding of H, other impurities , crystallinity, and morphologymay also affect the electrical properties (Section S3.3).AC Hall effect measurementswere performed to understand the origin of the resistivity changes.Carrier densities of both of the H0.80 process,that is, approximately 0.3 cm2 V–1 s–1. The improved mobility may be due to decreased chargecarrier scattering as a result of both a lower carrier concentrationand improved crystallinity compared to the A B0.80 process.The decreased carrier densities and increased mobilities over previouswork give promise for semiconductor applications, especially plastic-basedflexible electronics requiring a very low thermal budget. The smoothmorphology of the 10(A B0.20) CH2 process appearsto be particularly suitable for electronics.Furthermore, the Hall mobility of the three ABCprocesses was anorder of magnitude higher compared to the A B2.415 Here, we deposited approximately 7 nm thickMoS2 films on glassy carbon (GC) substrates by using ourthree ABC processes. 2SO4. The most commonly used activity metric is the overpotentialη required to reach a current density of 10 mA/cm2, which we denote η10.64 As the thermodynamic potential for HER is 0 V versus RHE, this isequal to the absolute value of the (negative) potential applied atthis current density. The lowest η10 value of 406mV was observed for the A B0.20 CAr processfollowed by the 10(A B0.20) CH2 (484 mV) andA B0.20 CH2 (573 mV) processes  of the 10(A B0.20) CH2 (115mV/dec) and A B0.20 CAr (123 mV/dec) processeswere lower compared to those of the A B0.20 CH2 process (165 mV/dec), which also required the highest overpotential.ElectrocatalyticHER is a commonly explored TMDC application, which benefits from thepresence of defects such as crystallite edges and vacancies that havebeen identified as catalytically active sites.rocesses 2. The HE2 catalysts, double layer capacitance (Cdl) of the films was measured by scanning potential in the non-Faradaicregion at varying scan rates . The measured Cdl values increased in the order of increasing HER activity(decreasing η10). Cdl is proportional to the density of double layer adsorption sites,which appears to correlate here with the density of HER active sites.Indeed, normalizing the current densities by Cdl brought the activities of different samples closer to eachother .To rationalize the differences in activity betweenthe differentMoSCdl produced by theA B0.20 CH2 process may result from its largestgrainsize and orientation of most of the MoS2 crystallites parallelto the substrate  CH2 films may providea higher accessible edge site density due to a smaller grain sizeand larger spread in the crystallite orientation. In addition, themore disordered structure suggested by Raman and TEM may indicatean increased number of active (defect) sites on the basal planes.Combining the clearly highest Cdl togetherwith the lowest η10 as well as the S-rich compositionsuggests that the A B0.20 CAr films containdisordered c-MoS2 domains and potentially even active-site-richnanoscale a-MoSx2+ clusters.66 This makes the Ar plasma based process the preferred choice forHER.The lowest ubstrate 7a. The f2 thin films on flat, inert substrates.68 This greatly exceeds the activity of bulkMoS2 (η10 > 1000 mV),68 but falls short of the best MoS2 catalysts takingadvantage of, for example, vacancy engineering and strain, which canachieve η10 approaching 150 mV ALD to improve catalytic activity.The overpotentials and Tafel slopes of our three catalystsfallin the range reported for nanocrystalline, relatively smooth MoSmV  CH2) appears particularly suitablefor (opto)electronics. The control of morphology and exposure of finsand grain boundaries achieved by different plasmas is of interestfor flexible gas sensors. The different ABC processes exhibit differentlevels of activity for electrocatalytic HER, which can be linked tothe film morphology and crystallinity. The Ar plasma process displaysthe highest HER activity stemming from active sites, such as crystalliteedges and other defects. The flexibility, scalability, and low thermalbudget of our approach gives ample opportunities for further expandingthe ABC process toolbox to tailor MoS2 and other TMDCsfor electronics, catalysis, and other applications.We developed a toolboxof advanced PEALD processes depositingwafer-scale polycrystalline MoS44.1x thin films were deposited by PEALD using an Oxford InstrumentsFlexAL PEALD reactor equipped with a remote 13.56 MHz inductivelycoupled plasma (ICP) source. The chamber was pumped with a turbomolecularpump capable of reaching a base pressure of 1 × 10–6 Torr. Unless otherwise noted, the table and wall temperatures wereset to 150 °C, meaning that the reactor acted as a hot wall reactorwith a substrate temperature of 150 °C. For experiments at highertemperatures, only the table temperature was increased, while forlower temperatures both the table and wall temperatures were set tothe indicated temperature. The films were deposited on silicon(100)substrates with a 450 nm wet thermal SiO2 layer on top(Siegert Wafer). In most cases, approximately 1 × 1 to 3 ×3 cm2 coupons were used on an 8 in. carrier wafer thatwas introduced into the chamber through a load lock. After transfer,the substrates were let to thermally equilibrate for 5 min beforestarting the deposition.MoStBu)2(NMe2)2 dosing at 200 mTorr,the B step of 20 s H2S/H2/Ar plasma exposureat 6 mTorr, and the C step of an additional Ar or H2 plasmaexposure  Cy. Unless otherwisenoted, both the B and C steps are plasma steps.The processes are denoted A BtBu)2(NMe2)2 precursor was heated to 50 °C in anexternal canister and supplied to the chamber by Ar flow throughdelivery lines that were heated to 70 °C to prevent condensation.The flow rates of H2S (99.5%), H2 (99.999%),and Ar (99.999%) gases supplied by Linde gas were controlled by massflow controllers. The pressure was controlled either by gas flows(1–20 mTorr) or an automatic butterfly valve (36–300mTorr).The Mo.Experiments using RF substrate biasing4.2in situ SE, either M-2000FI  or M-2000F by J.A. Woollam. Typically,film thickness was measured every 10 cycles. For evaluation of growthmechanisms, measurements were performed after each B and C step. Fordepositions without an in situ SE, film thicknesseswere measured ex situ after deposition using a variableangle J.A. Woollam M-2000U instrument . The SE modeling procedure was describedin our previous work.39 A B-spline modelwith 0.3 eV resolution was used to describe the MoS2 films.Film thicknesseswere measured by spectroscopic ellipsometry (SE). During most of thedepositions, the reactor was equipped with an Ex situ uniformity mapping was performed usinga J.A. Woollam M-2000 instrument equipped with an automated mapping stage. A circular pattern excludingareas close to the wafer edges was used.Rq) value from 500 × 500 nm images afterfirst order flattening using Bruker Nanoscope 2.0 software.Film morphology wasexamined by scanning electron microscopy  using an InLens detector and acceleration voltage of3 kV. Additionally, morphology and surface roughness were analyzedby atomic force microscopy  in PeakForceTapping based ScanAsyst mode in air. Probes with a nominal springconstant of 0.4 N/m and a tip radius of 2 nm were used . Surface roughness was calculated as root-mean-square  measurements complementing the Raman analysiswere performed in symmetric θ–2θ geometry usinga Bruker D8 Discover diffractometer equipped with a Cu X-ray tube(Kα λ = 1.54 Å). Background was removed by fittinga cubic spline function to the data.Film crystallinity was evaluated by Raman spectroscopy  equipped with a 514 nm laser, 50×objective (NA = 0.75), and 1800 lines/mm grating. Six spectra using10 s accumulation time each were collected for each sample. Incidentlaser power was estimated to be 0.6 mW on the sample .All of the presented spectra were normalized to the intensity (area)of the Si mode at 520 cmhν = 1486.6eV) focused to a 400 μm spot on the sample. An electron floodgun was used during the measurements to minimize the charging effects.The binding energies were referenced by setting the adventitious carbonderived C–C/C-H component of the deconvoluted C 1s peak to284.8 eV. A pass energy of 20 eV was used for high-resolution spectra.Peak deconvolution was performed using Avantage software (Thermo Scientific)using Gaussian–Lorentzian (30% Lorentzian) sum functions witha Shirley-type background.Film composition was analyzedby X-ray photoelectron spectroscopy(XPS) using a Thermo Scientific K-Alpha spectrometer equipped witha monochromatic Al Kα source  and elastic recoildetection (ERD) measurements were performed by Detect 99 B.V.  using a 2 MeV He2 or C/Pt mask layer.Transmission electron microscopy(TEM) imaging was performed usinga probe-corrected JEOL ARM 200F instrument operated at 200 kV. Thecross-sectional TEM samples were prepared by FEI Helios Nanolab 600or 600i dual-beam focused-ion beam FIB/SEM instruments following astandard lift-out procedure with a SiOI–V curve measured by a four-pointprobe . Film resistivity was calculated by multiplyingthe sheet resistance by the film thickness measured by SE. To extractcarrier concentration and mobility, AC Hall effect measurements wereperformed in van der Pauw geometry on approximately 1 × 1 cm2 samples using a Lakeshore 8404 HMS instrument.Sheet resistance of the films was determined as the slope of an 4.32 thin films on glassy carbon (GC) plates . Prior to deposition, the GC plates were polished by using anaqueous dispersion of 50 nm Al2O3 nanoparticles(BASi) applied to a velvet polishing pad (BASi) followed by rinsingwith deionized water. The polishing procedure results in Rq ≈ 1–3 nm, which is similar to that ofMoS2 films. No signs of plasma damage or etching of theGC were observed after deposition.Electrochemicalmeasurements were performed using a three-electrode setup controlledby an Autolab PGSTAT302N potentiostat (Metrohm) and a custom-madeglass cell. Working electrodes were constructed by depositing 7 nmthick MoS2/GC sampleswere mounted to a custom-made poly(ether ether ketone) (PEEK) sampleholder exposing a 3.14 cm2 area of the sample. The holderwas connected to a rotating disk electrode (RDE) assembly. A graphiterod counter electrode was positioned in a separate compartment separated by a glass frit.A commercial saturated calomel electrode  referenceelectrode was located in another glass-frit separated compartment.A Luggin capillary was used to position the reference electrode close(∼0.5 cm) to the working electrode.The MoS70 Thereference potential determined by this method was then used to convertthe measured potentials to a reversible hydrogen electrode (RHE) scale.Prior to use in thecatalytic measurements, the SCE was externallyreferenced to ferrocenecarboxylic acid in 0.2 M phosphate buffer titratedwith NaOH to pH 7 (284 mV vs SCE).2SO4 electrolyte (pH 0.3) prepared from concentrated H2SO4  and ultrapure water (resistivity18.2 MΩcm). The electrolyte was purged by bubbling N2 for at least 30 min prior to measurements. During measurements,the gas flow was switched to purge the headspace above the electrolyte.The cell was filled with ∼100 mL of 0.5 M HiR postmeasurement compensation of the measured CVs. Then,a set of CV scans were performed in an inert potential window (−0.2to 0.4 V vs SCE) to estimate the initial double layer capacitance(Cdl). In these measurements, the scan rate was increasedfrom 50 to 250 mV/s in 50 mV/s increments with three scans recordedper scan rate. Next, five cyclic voltammetry (CV) scans in the HERregion (−0.2 to −0.9 V and back vs SCE) were recordedat a scan rate of 10 mV/s while the electrode was rotated at 1600rpm. The data from the fifth scan were used to extract the overpotentialsand Tafel slopes (reported after iR compensation).Following these scans, the rotation was stopped, and visible bubbles(if any) physically removed with a glass pipet, followed by a secondset of CV scans in inert region  to estimate Cdl. This latter set of scans was used for determiningthe presented Cdl values, as these weretaken to better correspond to the sample state during HER comparedto the measurements performed before HER. Cdl was determined as the slope of the line fit to current densitiesof anodic scans at 0.4 V vs RHE at different scan rates.Measurement procedure began with an electrochemical impedance spectroscopy(EIS) measurement . The impedance of the data point with phase closestto 0  was taken as the uncompensatedresistance  and was used for 100%


Carbon-coated Mn-doped Li2Mn0.1Ti1.9(PO4)3 materials was synthesized by spray drying method. The material was characterized by XRD, SEM, TEM, BET, TGA et al. Crystal data refinement results by Rietveld method showed that the symmetry space group is Pbcn.The lattice parameters of Li2Mn0.1Ti1.9(PO4)3 are a = 11.9372 Å, b = 8.5409 Å, c = 8.5979 Å, α = β = γ = 90°, V = 876.59 Å3 and Z = 4). Rietveld refinement was performed, and the confidence factors are Rwp = 11.79%, Rp = 9.14%, and χ2 = 1.425. It was exhibited that LMTP0.1/CA-700 material has good crystallinity. Testing the cells with LAND test procedure (200 mA/g current density for 200 cycles), the LMTP0.1/CA-700 material has a discharge specific capacity of about 65 mAh/g. The capacity decayed by only 3% during the cycle. It has some potential application values as cathode of lithium ion battery in the future.The hunt for a higher power storage, relatively inexpensive, non-polluting battery technology is currently a pressing issue because of the rapid growth of the worldwide economic and the progressively significant environmental pollution. Among the possible nanomaterials for rechargeable batteries that can have heteroatoms applied to it in order to improve its electrochemical behavior is Li The synthesized materials were subjected to a series of characterizations such as XRD, SEM and TEM to test the morphological structure of the materials. Cells with different electrolyte systems were assembled and tested for their electrochemical properties.Mnoped FeS , Mn-dopeed FeS 3  has the  Fe, Cr)  and Li2FZr(PO4)3 , which hZr(PO4)3 . In this2PO4), lithium acetate (CH3COOLi⋅H2O), manganese acetate (Mn(CH3COO)2⋅2H2O) and Dihydroxybis (ammonium lactato)titanium IV) (Ti(OH)2(OCH(CH3)COONH4)2) aqueous solution as raw materials. All starting materials were purchased from Sinopharm Chemical Reagent Co., Ltd  and Shanghai Aladdin Biochemical Technology Co., Ltd . LiH2PO4, CH3COOLi⋅H2O and Mn(CH3COO)2⋅2H2O were dissolved in 300 mL of pure water according to a certain stoichiometric ratio, and the corresponding proportion of aqueous Dihydroxybis (ammonium lactato)titanium IV) solution was added under stirring conditions. After stirring for 30 min, spray drying was carried out. The spray drying program was set to 240°C at the inlet and 15 rmp at the feed rate, and the feed was started after the outlet temperature was above 85°C. After spray drying, the precursor material is obtained, and the precursor material and carbon source anhydrous citric acid are weighed and mixed in a certain ratio. The mixed material was added to the porcelain boat and heated up to 600°C, 700°C and 800°C in a tube furnace at a certain heating rate (4 °C/min) for 4 h. The final black solid powder  was obtained.Lithium dihydrogen phosphate  was used to observe the morphology of the material. High-resolution transmission electron microscopy  were used to research the microstructure of the samples. The carbon content of the sample can be known by Thermogravimetric Analysis (TGA). X-ray photoelectron spectroscopy  to indicate the structural valence of the materials.2 and the loading of active material is about 2 mg/cm2.The carbon-coated LMTP composite, Super P, and PVDF were weighed in a mortar according to the mass ratio of 7:2:1, and then ground and mixed. The milled electrode slurry was evenly coated on the collector  and placed in a vacuum drying oven. The drying conditions were 110°C/12 h. The dried electrodes were rolled with a roller press. The area of each working electrode is 1.15 cm2O4, Super P, and PVDF were mixed in the mass ratio of 75:15:10 and ground well. After that, an appropriate amount of NMP was added to it, and the grinding was continued for a certain time, and the ground slurry was evenly coated on the stainless steel. The coated stainless steel with electrode material was dried in a vacuum drying oven at 100°C for 12 h. The dried electrodes were rolled and then sliced. The area of the cut single electrode is 1.15 cm2 and the loading of its active material is about 2 mg/cm2.LiMn2O/O2 concentrations less than 0.1 ppm, using lithium cells as counter electrodes, the diaphragm was a common celgard 2,400 diaphragm, and the electrolyte used was 1 M LiPF6 organic solution, in which the volume ratio of solvent EC:DEC:DMC was 1:1: 1.Organic lithium-ion battery assembly: To assemble the organic lithium-ion battery, the button cell (CR2016 type) was assembled in an Ar-filled glove box with both H2Mn0.1Ti1.9(PO4)3 and LiMnPO4, and their mass fractions are 57.36% and 42.64%, respectively. Among them, the space group of Li2Mn0.1Ti1.9(PO4)3 is Pbcn and the corresponding lattice parameter a = 11.9372 Å, b = 8.5409 Å, c = 8.5979 Å, α = β = γ = 90°, V = 876.59 Å3 and Z = 4). Rietveld refinement was performed 3 and LiMnPO4  were shown in The XRD plots of the materials obtained by sintering at different temperatures are shown in erformed , and theSEM characterization was performed for the LMTP0.1/CA materials made at different temperatures to observe their morphology. To further characterize the specific morphology of LMTP0.1/CA-700 material, TEM was used to characterize the structure of the material, as shown in 1s, with a total of three strong peaks corresponding to the three chemical bonds C=O (288.40 eV), C-O (286.14 eV) and C-C or C=C (284.80 eV) , Ti3+2p1/2 (463.88 eV), Ti4+2p3/2 (460.38 eV) and Ti3+2p3/2 (456.68 eV)  , and theterature . Two dis6.68 eV) , respect2/g  and the scan rate was 0.1 mV/s. As shown in The electrochemical reversibility of the LMTP0.1/CA electrode materials sintered at different temperatures was tested separately using cyclic voltammetry, as shown in +/Li). From To further understand the cycle reversibility performance of the LMTP0.1/CA-700 composite, the material was tested for 3 cycles under the same conditions, and the results are shown in + diffusion resistance is reduced. As expected, the increase in temperature is beneficial to the improvement of the material properties, however, too high temperature may damage the structure of the material, which is not conducive to the enhancement of the electrochemical properties of the material.Lithium-ion batteries were assembled using lithium sheets as counter electrodes. From the above data, it can be seen that the LMTP0.1/CA material can maintain good cycle reversibility and high Coulomb efficiency in both charge and discharge constant cycle tests at high current density. However, the electrochemical performance of the LMTP/CA-700 material is better compared to the remaining two materials at temperature due to its highest discharge specific capacity. The material produced at 600°C and 800°C has a lower specific discharge capacity when the current density becomes higher. Therefore, 700°C is the best preparation condition for this material.4, however, the scientific contribution of this Mn-doped phosphate series materials provides a direction for more in-depth and extensive research in order to make a breakthrough in the mechanism and find the most optimized technological parameters required for better electrochemical performance.Looking at the electrochemical performance of all batteries with synthetic materials as the positive electrode and lithium flakes as the negative electrode, it can be found that the LMTP0.1/CA material sintered at 700°C with anhydrous citric acid as the carbon source has the best electrochemical performance and can maintain a more stable capacity even at higher current densities. This specific capacity still has a lot of optimizing space compared to that of the commercial battery material LiFePO+. The half-cells were assembled with the synthesized materials as the positive electrode, and the CV curves showed three reaction platforms for each of the synthesized materials. Testing the cells with the same LAND test procedure (200 mA/g for 200 cycles), the LMTP0.1/CA-700 material has a discharge specific capacity of about 65 mAh/g. The capacity decayed by only 3% during the cycle.In this paper, LMTP0.1/CA composites were prepared by spray drying method and subjected to conventional characterization and electrochemical performance tests. The XRD and SEM results showed that the LMTP0.1/CA-700 material has good crystallinity, and the SEM patterns showed obvious spherical particles. The BET showed that the pore size of the material is of micro-nanometer level, which facilitates the entry and exit of LiThe full cells with 600°C and 700°C sintered materials as negative electrodes decayed less under the same test conditions (200 mA/g for 200 cycles), but the specific capacity of LMTP0.1/CA-700 (60 mAh/g) was about 20 mAh/g higher than that of LMTP0.1/CA-600 (40 mAh/g), while LMTP0.1/CA- 800 has a higher initial specific capacity, but decays faster during cycling, decaying by 12%. It indicates that LMTP0.1/CA-700 material has better performance when used as anode material for water-based batteries. Through the above structural characterization and electrochemical tests, the material made by sintering at 700°C has the best morphology and the best electrochemical performance. This may be due to the poor crystallinity of the material when the sintering temperature is too low and the internal collapse of the material structure when the sintering temperature is too high. Future research will focus on the doping element type, ratio and preparation control condition, which also provide a potential research idea for the better battery material of phosphate system, and also show from the side that the doping element will have a significant contribution to the electrochemical performance of the battery material, and this series material will also have an extensive electrochemical application value.


The spectral analysis of the obtained cellulosic derivatives was confirmed with FT-IR, NMR, and SEM. Additionally, a neutral red uptake analysis has been used to investigate the cytotoxic activity of the cellulosic compounds MDAC(2), MDAU(4), and MDAP(5) against the cancer cells A549 and Caco2. After 48 h, Compound MDAU(4) had a stronger inhibitory effect on the growth of A549 and Caco2, compared to standard values. Then, using QRT-PCR, the appearance sites of the genes -Catenin, c-Myc, Cyclin D1, and MMP7 in A549 cells were examined. By reducing the expression levels of the Wnt signaling cascade genes -Catenin, c-Myc, Cyclin D1, and MMP7 when administered to A549 cells, compound MDAU(4) was shown in this investigation to be a viable candidate compared to lung cancer. Additionally, docking simulation was used to explore the uracil cellulosic heterocycles attached to different proteins, and computational investigations of these compounds looked at how well their physical characteristics matched the outcomes of their experiments.In this study, the oxidation of microcrystalline cellulose using NaIO Furthermore, Lung tumor is one of the maximum popular cancers internationally, and it is disturbing in males and females10. Wnt/β-catenin signaling pathway is an important molecular cascade in modified embryonic development and adult homeostasis14. However, it has been implicated in multiple human malignancies, including colorectal cancer, breast cancer, prostate cancer, and non-small cell lung cancer, due to dysregulation18. Beta-catenin is one of a big and complicated array of proteins which it's involved in the control of the Wnt/β-catenin signaling pathway19. Also, the dissociation of beta-catenin from this destruction complex outcomes in the aggregation of beta-catenin in the cytoplasm and nucleus, which activates the target genes of the Wnt pathway, such as cyclin D1, MMP7, and c-Myc in human cancers21. In this elucidation, we synthesized the novel pyrazole cellulosic compounds from the reaction of condensation with cellulose aldehyde with active CN-uracil acetamide to give the corresponding cellulose arylidene MDAU(4). This compound can then be easily cyclized in the presence of nitrogen nucleophiles like hydrazine hydrate to give the pyrazole cellulosic derivative MDAP(5), which was confirmed through spectral analysis. Additionally, we examined these cellulosic derivatives with cytotoxic effects on lung cancer cells (A549) and colon cancer cells (Caco2), and we then examined the levels of -Catenin, Myc, Cyclin D1, and MMP7 gene expression in A549 cells. The heterocyclic cellulosic compounds were also docked with the PDBID:2ito, 1nun, 5jsn, and 5vzu, respectively. Additionally, the cellulosic compounds were improved utilized the DFT/B3LYP/6-311(G) basis set, which demonstrated the stability of the compounds as a result of the interaction of the NH and OH of cellulose, uracil, and pyrazole in electrostatic hydrogen bonds24.The waste minimization of agriculture waste takes the attention of most scientists due to the presence of cellulosic bone which has chains comprised β(1 → 4) linked to D-glucose1H NMR and 13C NMR spectra were determined in DMSO-d6 at 300 MHz on a Varian Mercury VX 300 NMR spectrometer  exhausting trimethyl silane as an internal typical. Scanning electron microscopes (SEM) were investigated utilizing JEOL JXA-840A electron probe Microanalyzer Company and were air-dried before imaging, and images were obtained using an accelerating voltage of 10–15 kV. In closed vessels under pressure, microwave-irradiated Pyrex tubes with caps were used to conduct the reactions.The Shimadzu FT-IR 8101 PC infrared spectrophotometer recorded the IR spectra. The 2NH2, triethyl amine, purchased from Aldrich Chemical Company. 2-cyano-N-acetamide(3) was synthesized according previous procedure25.Microcrystalline cellulose (20 μm) was obtained from the Rasyan research laboratory, and NaIO4 was ordered from Fluka. EtOH, NH26, through the basic response of Schiff. NH2OH.HCl is used when aldehyde groups transform into oximes. Dialdehyde cellulose, 0.3 g, was dispersed in 20 ml of pH-5 NaOH solution-containing water, then, NH2OH.HCl (0.72 mol/l) was added at pH 5 for 4 hours, the mixture was stimulated at 40 °C. To titrate the emitted HCl, a 1.0 M aqueous NaOH solution was used. The volume of alkali solution consumed during the titration was recorded (in liters), and the amount of NaOH consumed when the pH value of the solution reached 5.0 was validated. The volume of 1.0 M sodium hydroxide solution consumed was measured as Vc (in liters), using the same concentration of cellulose solution at pH 5.0 as a blank. The following equation is used to designate the aldehyde content (% w/w)28.NaOH = 1.0 M, m is the dry weight of DAC (0.3 g) used in the experiment, and M molecular weight of the repeating unit of cellulose (162).Using a microwave device, cellulose was oxidized to various degrees of oxidation with NaOI4 (20 ml). At 3, 1, and 1.5 min, the precursor was transferred to the microwave to finish the oxidation process. The oxidized product was filtered, EtOH washed, and allowed to dry for a whole night at room temperature. Using 1.5 g of cellulose and 20 ml of distilled water, aldehyde concentration was determined2)  was mixed with 2-cyano-N-acetamide(3) in EtOH and 2 drops of triethylamine as basic catalyst were refluxed for 5 h at 120 °C and monitored through TLC with (ethyl acetate/petroleum ether) eluent(1:1) then the product filtered off and recrystallized from EtOH/H2O to afford the corresponding (Z)-2-cyano-N--5,7-dihydroxy-6-(1-hydroxy-2-oxoethoxy)hept-2-enamide (4): colorless powder, m.p =  > 300 °C, FT-IR (KBr): ν 3410(OH), 3352(NH), 3200(NH), 3174(NH), 2990 (CH2), 1650(C=O),1550(C=C); 1H-NMR (DMSO-d6): δ 3.54, 4.02, 6.6 , 7.02,7.9 , 7.5 , 8.96 ,10.32 11.62, 13CNMR(DMSO-d6), δ 28(CH2), 66(CH2), 77(CH2), 88(CH2), 100 (CH=), 110(CH), 115(CN), 134(CH),150(CH=),160(C=O), 169(CH=).Stirring solution of MDAC(4)  with hydrazine hydrate (1 mmol) was heated for 6 h, then left to cool and monitored through TLC with (ethyl acetate/petroleum ether) eluent (1:!) then the product was formed and filtered off, washed with ethanol, and dried. Recrystallization from DMF/H2O to give 3-amino-5-propyl)-N--1H-pyrazole-4-carboxamide(5): yellow powder, m.p =  > 300 °C, FT-IR (KBr): ν 3455(OH), 3400(OH), 3364(NH), 3305(NH), 3214(NH), 3204(NH), 3175(NH2), 2990 (CH2), 1715(C=O), 1655(C=O), 1599(C=O), 1510(C=C), 1H-NMR (DMSO-d6): δ 3.65, 4.11, 5.21 , 6.35 , 7.5 , 9.52 ,10.02,11.20 , 11.52, 12.01, 13CNMR(DMSO-d6), δ 55(CH2), 84(CH2),100(CH2), 112 (CH),135(CH), 141(CH),155(C=O),160(C=O), 164(C=O), 177(C=O).Reactivity of MDAU(A549 and Caco2 cell lines were acquired from (American Type Culture Collection) and conserved in suitable conditions. A549 cells were refined in DMEM (Dulbecco’s modified Eagle’s Medium) and Caco2 cells were cultured in RPMI Medium containing 10% fetal bovine serum (FBS), 100 U/ml penicillin, and 100 μg/ml streptomycin sulfate at 37 °C in a humidified 5% CO2. The cells were digested with 0.025% trypsin-EDTA for passaging. The cells in the logarithmic growth phase were used in the experiment. The cytotoxicity of uracil pyrazole cellulosic compounds was examined via a neutral red uptake method. Several concentrations  of heterocycles were added to continue the culture for 48 hours at a cell density of 104 cells/well of 96 well plate and neutral red uptake assay was done as reported by Repetto et al.29. The relative between the used log concentrations and the neutral red intensity value accustomed estimate half maximal inhibitory concentration (IC50) of heterocycles. The medium was added instead of the cellulosic heterocycles for the untreated cells (negative control). A cytotoxic natural agent  was used as positive control giving 100% inhibition. Cellulose products were dissolved in DMSO and its final concentration was not increased than 0.2% in the cells. All analyses were achieved at least three times.A549 cells (3 × 104 cells/well) and treated for 48 h using RNA easy mini Kit  then the concentration and purity of total extracted RNA were determined using NanoDrop one micro-volume UV spectrophotometer . RNA of each treatment was converted to first-strand cDNA according to manufacturer instructions using Revert Aid First Strand cDNA Synthesis Kit . Specific primer sequences are listed in Table β-Catenin, c-Myc, Cyclin D1, and MMP7 genes were normalized concerning β-actin transcript using Maxima SYBR Green qPCR Master Mix (2X)  and calculated by 2−ΔΔCT method59. The reaction conditions were as follows: 95 °C for 10 min, 95 °C for 15 s, 60 °C for 30 s and 72 °C for 30 s with a total of 40 cycles of amplification. DNA Technology Detecting Thermocycler DT Lite 4S1 was used for gene expression quantitation.RNA was isolated from P < 0.05.Outcomes are expressed as Mean ± SEM. Statistical analyses of the data are achieved utilizing Sigma plot ver. 125. Student t-test was used to analysis of the data and distinguish the noteworthy change among the studied heterocycles. Changes were considered significant when 30 to confirm the biological action and communication with them concluded different binding proteins such as Crystal structure of EGFR kinase domain G719S mutation in complex with Iressa (PDBID:2ito)31, Crystal Structure Analysis of the FGF10-FGFR2b Complex (PDBID:1nun)32, Bcl2-inhibitor complex (PDB ID: (5jsn)33 and Crystal structure of the Skp1-FBXO31-cyclin D1 complex (PDB ID: (5vzu)34; correspondingly. For separate proteins, 9 dissimilar docking simulations were operate utilized default limits35.Dockage of uracil cellulosic heterocycles using the MOE program36 was used for the geometry optimization38. The majority benefit of DFT methods is that they afford a substantial growth in computational accurateness lacking increasing computation time. All chemicals were imagined via Gauss-View39. Physical limitations were evaluated using the EHOMO and ELUMO values, while other limitations were retrieved from files41.Uses of the gas phase of DFT/B3LYP/6-311(G) level utilized Gaussian 09 program1) with sodium hypochlorite utilized Microwave irradiation MDAC(2) in excellent yield, the formation of cellulose aldehyde MDAC(2) was confirmed through previous studies42 and determination of cellulose aldehyde content, the reactivity of cellulose aldehyde MDAC(2) was so reactive which has methyl group which easily of attack with any active methylene group,  as displayed in Fig.2) with 2-cyano-N-acetamide(3) in equal amounts to afford the corresponding (Z)-2-cyano-N--5,7-dihydroxy-6-(1-hydroxy-2-oxoethoxy)hept-2-enamide MDAU(4) and confirmed through FT-IR which showed 3410 cm−1 for hydroxyl group and more NH group at 3352-3174 cm−1 due to presence of uracil moiety and 2250 cm−1 for C≡N group, also the 1HNMR showed CH=olefin hydrogen of arylidene at δ = 10.32 ppm and more exchangeable proton at OH and NH of glycoside and uracil moieties at 4.02, 8.96, 11.62 ppm; respectively. Furthermore, the reactivity of arylidine MDAU(4) due to the presence of olefin hydrogen adjacent to the C≡N group which can be easy to cyclized in the presence of nitrogen nucleophiles such as NH2NH2, also the reactivity of MDAU(4) with hydrazine hydrate refluxing in EtOH to afford the corresponding 3-amino-5-propyl)-N--1H-pyrazole-4-carboxamide MDAP(5) and showed the stretching absorption band at 3175 cm−1 for an amino group of the pyrazole ring and more of NH bands at 3364–3204 cm−1 and the NMR showed exchangeable protons of NH2 group at 11.20 ppm and the NH protons were dishelded in 11.52, 12.01 ppm, and the 13CNMR showed the three carbonyl bonds from the range at 155–177 ppm; respectively as demonstrated in Fig. Oxidation of microcrystalline cellulosic ring MCEC with sod4), and Pyrazole cellulose MDAP(5) as displayed in Figure 2) showed a characteristic absorption band of C=O at 1650 cm−1 represents to two aldehyde group, and these bands can be so small or hidden in hydrated form but there is hemiacetal group which confirms the presence of aldehyde group. Furthermore, the presence of an adsorption band at 800–750cm−1 conforms to the hemiacetal bond which is a typical peak of aldehyde28. Moreover, the MDAU(4) showed a characteristic beak of the presence of three NH bands in the range 3352–3174 cm−1 due to uracil moiety, and the C≡N group showed bands at 2250 cm−1, carbonyl group at 1650 cm−1 and more CH stretching vibration at 2990 cm−1 for uracil and glycoside ring, also the MDAP(5) showed a wide range in OH vibration in 3455–3400 cm−1, and more bands for NH and NH2 which take the wide range in 3364–3175 cm−1 for amino pyrazole and uracil rings and cyano group is absent and there is more bending vibration for MDAU(4) and MDAP(5) for CH aliphatic of glucose and uracil and change the vibration of aldehyde cellulose.FT-IR of the novel synthesized cellulosic heterocycles was cellulose aldehyde MDAC2), arylidine MDAU as seen in Fig. Additionally, SEM examination of cellulose aldehyde presented the tight bundles crossed to each other and it changed the morphology of cellulose due to the oxidation process as shown in Fig. A549 and Caco2) at  concentrations via neutral red uptake analysis which is constructed on the ability of viable cells to include and bind the supravitally dye neutral red in the lysosomes. Doxorubicin (Dox) was used as a standard drug with IC50 values of 4.8 and 22.5 µM against tested cells (A549 and Caco2 respectively). The use of DMSO as a solvent had an insignificant effect on the viability of A549 and Caco2 cells when preserved for 48 h. Compared with control values, all heterocycles meaningfully affected cell growth inhibition. Data in Table MDAU(4) > MDAC(2) > MDAP(5) against A549 cancer cells. At 48 h, compounds MDAU(4) (17.3 µM) showed more inhibitory effects compared with starting MDAC(2) (59 µM) while compound MDAP(5) (89.7 µM) exerted a slight cytotoxic influence on A549 cells comparable with control values. Results explained in Fig. Caco2 tumor cells preserved with different concentrations of cellulose compounds after 48 h. All data in Table MDAU(4) > MDAP(5) > MDAC(2) contra Caco2 cells. The treatment of Caco2 cells with compounds MDAU(4) (89.26 µM) exhibited high cytotoxic activity as comparable with MDAC(2) (188.8 µM) after 48 h. Additionally, MDAP(5) with IC50 values of (150.24 µM) displayed moderate inhibition growth than MDAC(2) against Caco2 tumor cells in comparison with control values. Lastly, these outcomes exhibited that the cellulosic compounds MDAU(4) revealed more inhibitory effect compared to starting material and standard values once preserved with two tumor cells (A549 and Caco2) after 2 days44.Uracil pyrazole cellulose compound was investigated on the cell growth from two tumor cells (MDAU(4) is more effective and more cytotoxic than the presence of pyrimidinyl pyrazole carboxamide ring in MDAP(5) compared to the presence of dimethyl aminooxopentenenitrile ring in starting compound MDAC(2) when treated with A549 and Caco2 cells. These outcomes recognized the importance of the presence of uracil pyrazoles cellulosic compounds for anticancer activity as displayed in Fig. 646.SAR examination showed the activity of the combination of heterocyclic moieties with cellulose compounds participated in variation in the cytotoxic effect of these compounds. At 48 h incubation time, The presence of dioxo tetrahydropyrimidinyl hydroxyl butenamide moiety in compound 47. The less energies were then executed to preserve the geometrical optimization and systematic inquiries with an RMS gradient of 0.01 Å. Crystal structure of EGFR kinase domain G719S mutation in complex with Iressa (PDBID:2ito)31, crystal structure analysis of the FGF10-FGFR2b Complex (PDBID:1nun)32 as demonstrated which were occupied from protein data bank in Table 7. The active site of PDBID:2ito showed 95 sides and different residues of amino acids such as  as showed in Fig. , and the active site in protein PDBID:1nun showed 39 sides attached with amino acids such as  as displayed in Fig. PDBID:1nun also showed the most reactivity of the binding site of MDAU(4) with − 9.612 kcal/mol, and bond lengths 2.51 Å and displayed different interaction with amino acids through electrostatic hydrogen bond interaction . Furthermore, the MDAP(5) showed moderate activity in both proteins with energy − 8.524, − 10.052 kcal/mol; respectively for PDBID:2ito and 1nun and bond length 1.58–3.06 Å with amino acids , ,  and  which showed most interaction from OH of glycose of the cellulosic chain as presented in Fig. Moreover, the docking simulation of uracil pyrazole cellulose was improved with bond lengths in Å units via the Moe programFrom the above results, we concluded that the presence of uracil acetamide attached to cellulosic moiety increased the electrostatic hydrogen interaction and presence of NH, C=O enhanced this activity, and the presence of pyrazole uracil cellulosic derivatives enhanced the biological evaluation and docking result confirmed the biological evaluation.A549 cells preserved with uracil pyrazole cellulose MDAC(2), MDAU(4), MDAP(5) on mRNA expression levels β-Catenin, Myc, Cyclin D1, and MMP7 genes were estimated utilizing IC50 standards of these heterocycles later 2 days and were estimated through calculating the percentage of its expression to that of β-Actin and in comparison to control values. From earlier analysis, it is fit recognized that the expression levels of β-Catenin, Myc, Cyclin D1, and MMP7 are up-regulated in A549 cells49. The Wnt signaling pathway is a complex pathway that regulates cell growth and proliferation50. The abnormal excitation of the pathway due to genetic mutation or increased stability can activate the abnormal expression of downstream target genes, including, Myc, Cyclin, and MMP-7, which can lead to cell proliferation, inhibition of cell apoptosis, and tumor formation51. Canonical Wnt/β-catenin pathway stimulates gene transcription through β-catenin52. MYC proto-oncogene amplification is closely related to tumor formation, development, and metastasis and is highly expressed in cervical cancer, breast cancer, gastric cancer, and other tumors41. Cyclin D1 considerably contributed to the development of the G1 to S phase53. The previous studies showed that the MMP-7 expression has been closely associated with tumor invasion and metastasis54. The current results showed that doxorubicin decreased significantly the expression levels of β-Catenin, Cyclin D1, and MMP7 genes in A549 cells as compared to control values  and MDAP(5) resulted in a significant reduction in levels of MMP7 and c-MYC genes in comparison with control values. Besides, compound MDAU(4) exhibited a significant reduction in levels of β-Catenin, Myc, Cyclin D1, and MMP7 genes in A549 cells compared to control values  is the most promising anticancer agent against A549 cancer cells through the reduction of expression levels of β-Catenin, Myc, Cyclin D1, and MMP7 genes compared to control values50.The ues Fig. . On the ues Fig. . From obPDBID: (5jsn)33 and Crystal structure of the Skp1-FBXO31-cyclin D1 complex PDBID: (5vzu)34; respectively. Figure Additionally, uracil pyrazole cellulosic were interact with two types of proteins, particularly for genes for instance Bcl2-inhibitor complex 2 of pyrazole ring as demonstrated in Fig. The docking analysis of PDBID:5jsn showed 50 sides with different residues  which is uracil pyrazole cellulosic displayed excellent outcome with MDAU(4) with high binding with − 9.412 eV and shortage bond length  and dissimilar amino acids  and the MDAP(5) showed − 8.724 kcal/mol and its length and linked with  which attached with OH and C=O and MDAC(2) showed least binding affinity with − 8.32 kcal/mol with 1.67, 1.69, 2.81 Å and amino acids Lys 22, Gln 25, Asp 102, Arg 26 which indicate the presence of these cellulosic heterocyclic inside the pocket of protein. Moreover, the interaction of cellulosic heterocyclic with PDBID:5vzu showed 75 sides of reactivity with amino acids   level. Besides, physical features of molecular structures of MDAC(2), MDAU(4), and MDAP(5) were regarding (σ) softness57, (χ) electronegativities58, (ΔNmax) electronic charge59, (η) hardness, (ω)60 electrophilicity61, (S) softness62, and (Pi) chemical potential64, from the equations (1_1059The Gaussian(09) program was used for uracil pyrazole heterocycle optimization66,Moreover, the uracil heterocycles exhibited the non-planarity with DFT/B3LYP/6-311(G) level, and MDAC(2) showed total energy of it was  with coplanarity of two carbonyl group in glycoside ring and they were far of each other and blinded with each other with hydrogen bonds which make the band energy gap with ∆E = 3.97262 eV and this high gap gave the aldehyde stability and ability to interact again with other compound and as demonstrated in Fig. 42. This is demonstrated in Fig. 69, According to Fig. 73. Due to the formation of pyrazole attached to cellulose with , its HOMO–LUMO delocalization of charge on pyrazole and uracil rings and lack of delocalization on OH group of glycose ring, as well as the presence of NH and carbonyl of pyrazole uracil, the MDAP(5) demonstrated greater stability than MDAU(4), gave it stability, its band energy gap was 0.95948 eV, and the charge energy departure of its dipole moment was 2.5425D. As a result, the MDAP(5) displayed high electrophilic attractiveness with 6.980 eV and electronic charge ΔN max with 5.39 eV due to more NH and NH2, which increased the electronic charge75 on it as shown in TableAdditionally, the energy of the cellulosic compound MDAU(4) is more stable than MDAC(2) with  due to the presence of the uracil moiety connected to MDAC(2) and more NH groups, which increase the stability of the molecule50 values and the largest cytotoxic activity against A549 and Caco2 cells in comparison to the beginning compound MDAC(2)47. The Wnt genes  are likewise expressed at lower levels in A549 cells after 48 h. Additionally, the docking stimulation revealed that MDAU(4) had an excellent binding affinity for the majority of proteins with the least amount of energy required due to the presence of more NH and OH in its structure. These findings were further supported by the physical descriptors of these cellulosic compounds, which demonstrated the stability of these compounds due to increased hydrogen bonding interaction.In this elucidation, the cellulosic aldehyde was combined with uracil acetamide to produce the corresponding arylidene cellulosic derivatives, which served as the active site for the nucleophilic addition to give the corresponding pyrazole cellulosic derivative. These heterocycles were then confirmed through various analyses, and it was discovered that more hydrogen bond interactions caused the binding to occur on the cellulosic surface. Additionally, the tested compound MDAU(4) displayed the lowest IC