Fabrication of Lignocellulose-Based Microreactors ... - ACS Publications

Research Article Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Fabrication of Lignocellulose-Based Microreactors: CopperFunctionalized Bamboo for Continuous-Flow CuAAC Click Reactions Druval Santos de Sa,́ † Rodrigo de Andrade Bustamante,‡ Carlos Eduardo Rodrigues Rocha,‡ Verônica Diniz da Silva,† Elton Jorge da Rocha Rodrigues,† Camilla Djenne Buarque Müller,† Khosrow Ghavami,§ Alessandro Massi,∥ and Omar Ginoble Pandoli*,† †

Departamento de Química, Pontifícia Universidade Católica, Rua Marque de São Vincente, 225, 22451-900 Rio de Janeiro, Brasil Departamento de Engenharia Química e de Materiais, Pontifícia Universidade Católica, Rua Marque de São Vincente, 225, 22451-900 Rio de Janeiro, Brasil § Departamento de Engenharia Civil, Pontifícia Universidade Católica, Rua Marque de São Vincente, 225, 22451-900 Rio de Janeiro, Brasil ∥ Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara, Via Luigi Borsari, 46, I-44121 Ferrara, Italy

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‡

S Supporting Information *

ABSTRACT: The fabrication of a new copper-functionalized lignocellulosic microreactor (Cu-LμR) from bamboo culms is herein described together with its operation to perform a copper(I)-catalyzed 1,3-dipolar cycloaddition between azide and terminal alkyne (CuAAC). The bio-microfluidic device showed an easy prototyping and fast functionalization with copper ions. All reactions were carried out in flow regime with aqueous-methanol solvent and minimal leaching of copper, yielding a series of model 1,4-disubstitued triazole derivatives with good efficiency in a low-resource setting.

KEYWORDS: Bio-microfluidic device, Click-chemistry, Heterogeneous catalysis, Bamboo, Sustainable microfabrication, Fast prototyping, Biomaterials

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INTRODUCTION The research on bio-microfluidics has shown to be promising for the application of biomaterials and biomimetic analogues as microfluidic devices (MDs), mainly for biosensing and biomedical studies.1 Nature is an important source of inspiration for scientists in understanding the complex relationship between structure and function of matter for the development of advanced technologies satisfying environmental requirements.2 Plants are one of the best sources to create advanced materials,3−5 specifically biopolymers (cellulose, hemicellulose, and lignin),6 which might be employed as the structural basis of functional MDs, such as paper-based microfluidic devices (PμDs),7 with some advantages compared to the common systems manufactured from elastomers,8,9 thermoplastic,10,11 glass,12 and metals.13 Plants allow nutrients to flow in and out of cells through hydrophilic microchannels in a water medium. In addition to the compatibility with a safe solvent, additional benefits of using plants and agricultural residues as a resource for microfluidic chip fabrication rely on the utilization of renewable, biodegradable, and biocompatible materials in full agreement with the green chemistry principles.14 Plant-derived microfluidic systems have never © XXXX American Chemical Society

been applied to synthetic processes for the production of target molecules, according to available publications.15 Microreactor technology (MRT) is targeting process intensification through the design of size-controlled microfluidic reactors with large surface-area-to-volume ratio to induce diffusion mixing of the reagents and fast dissipation of heat. MRT provides benefits in terms of reaction selectivity, yield, sustainability, and scalability of reaction by a numbering-up approach.16−20 Moreover, an important aspect is the reproducibility and low-cost production of MDs to establish a scalable fabrication technology for the potential industrial and academic market.21,22 This paper presents the results of an investigation related to the lignocellulose-based microreactors (LμRs), fabricated from vegetal resources, namely, bamboo culms, which are effectively operated to conduct environmentally benign chemical processes, expanding the toolbox of available microfluidic reactors for synthesis. The giant bamboo (Dendrocalamus giganteus Munro) is an abundant plant characterized by a high Received: October 12, 2018 Revised: December 7, 2018

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DOI: 10.1021/acssuschemeng.8b05273 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Figure 1. Fabrication of lignocellulose-based microreactors (LμRs) from bamboo internode 7.

Scheme 1. Functionalization with Copper Ions of LμR

growing rate (up to 30 cm day−1), low cost (ca. USD 0.009/ ea), and high ability to reproduce.23 Bamboo is a feedstock of biomass energy but also a raw material for textile, paper, and building industries. Bamboo is a composite material consisting of cellulose fibers reinforced in the lignin matrix. The polymers form microfibrils, which in turn are organized in macrofibrils to create the vascular bundles for nutrient and fluid transport.24 Bamboo-based analytical MD impregnated with colorimetric indicators has been presented for water and food assays.25 The present study is the continuation of the research on the incorporation of silver nanoparticles in natural bamboo for the improvement of antimicrobial activity to the native biomaterial.26 In the present investigation the hydrophilic microsized channels of bamboo have been doped with copper ions to run copper(I)-catalyzed 1,3-dipolar cycloadditions (CuAACs)27−29 for the continuous-flow synthesis of model 1,2,3-triazole derivatives in aqueous medium. In this work, the rapid, cost-effective prototyping of the disclosed copperfunctionalized lignocellulosic microreactor (Cu-LμR) also is

described together with a detailed analysis of the bamboobased biocomposite material.

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RESULTS AND DISCUSSION Fabrication and Characterization of LignocelluloseBased Microreactors. The sequences involved in the fabrication process of the lignocellulose-based microreactor (LμR) are depicted in Figure 1 (a tutorial video is also available in the Supporting Information). These consist of (i) cutting an internode sector of bamboo culm into a suitable segment length of 3 cm and 6 mm diameter, using three different types of rotary saws; (ii) cleaning the internal vascular bundles with water by vacuum-induced penetration and drying in a standard convection oven; (iii) reducing the diameter size of the segment to 4.2 mm; and (iv) gluing two syringe needles as inlet and outlet of the microreactor with connections to polyethylene tubes (0.86 mm i.d., 1.32 mm o.d.). Initially, the mechanical resistance of LμR was tested by injecting for 24 h (peristaltic pump) pure water at different flow rates (from 0.1 to 2.0 mL min−1; backpressure, 5.0 psi at B


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ACS Sustainable Chemistry & Engineering 2.0 mL min−1, Figure S1). Gratifyingly, no leaching at the device−connector interface was observed nor along the radial axis of the microreactor. Then, the known batch procedure for TEMPO-mediated oxidation of cellulose30 was adapted to the flow system by recirculating a TEMPO/NaBr/NaClO solution through the LμR for 4 h at a flow rate of 0.1 mL min−1 (Scheme 1 and the Supporting Information). This strategy allowed a chemoselective oxidation of the primary hydroxyl groups at the C6 of the D-glucose residues with formation of carboxylate functionalities, which are capable of complexation with copper ions.31−33 The functionalization of the internal walls of the micrometer-sized channels of LμR was achieved under flow conditions by continuously pumping a 0.10 mol L−1 CuSO4·5H2O solution for 2 h (flow rate: 0.1 mL min−1). The amount of loaded copper in the resulting copperfunctionalized lignocellulosic microreactor (Cu-LμR) was determined by evaluating the decrease of copper content (ICP-MS analysis) from the initial CuSO4 solution after recirculation (0.610 ± 0.063 mg, equivalent to 7% of copper used for the functionalization process, Table S1). Figure 2 shows the FT-IR-ATR spectra of slices of the initial bamboo-based microreactor (LμR), after oxidation and

carboxylate during the formation of the −COO−Cu(II) complex. The complexation of a carboxylate group with a metal can occur in three ways according to the separation of symmetric (sym) and asymmetric (asym) stretches (Δv = vasym − vsym): (i) monodentate chelator (200 Δv 320 cm−1), (ii) bidentate chelator (Δv 110 cm −1), and (iii) bidentate bridge (140 Δv 190 cm−).39,40 In this work it was not possible to identify the symmetric stretching of the carboxylate group in the complex because of the bamboo polymeric variety that absorbs in the range 1240−1510 cm−1; therefore it was not possible to determine the form of copper complexation on the inner wall of the microfluidic device. Then, the Cu-LμR was duly characterized by X-raycomputed microtomography (μCT) to analyze the process of copper deposition onto the bamboo microchannels (Figure 3, Table S3). The 2D and 3D μCT images of Cu-LμR showed different anatomic parts of the functionalized bamboo. The vascular bundle, which is composed of metaxylem (mean area 0.0193 ± 0.0081 mm2), phloem (mean area 0.0285 ± 0.0086 mm2), and protoxylem (mean area 0.0028 ± 0.0010 mm2), is an empty space and appeared in black color, while the parenchymatic living cell tissue resulted in dark gray.26 The higher-density sclerenchyma tissue, which is formed by crystalline cellulose fibers mixed with lignin and hemicellulose, is represented by a brighter gray color. The copper deposition onto the microarray of lignin-cellulose parallel channels was demonstrated in correspondence of the injection area by the white color in the middle of the dotted circular yellow line (4.2 mm i.d.), which corresponds to the internal area of the flow injection system (Figure 3A). The longitudinal cross-section (Figure 3B) showed a vertical white color along the total extension of the microchannel vascular bundles. Figure 3D displays the prospective 3D μCT images elaborated with a postprocessing software tool for fading the biomass structure and showing the copper deposition. The red dotted line highlights a single vascular bundle, and the inset image shows a layer of copper deposition of about 21 μm thickness. It is worth noting that most of the deposited copper ions penetrated inside the sclerenchyma tissue, thus preventing significant leaching of metal ions in the subsequent catalytic flow processes (vide infra). Moreover, the carboxylation procedure partially destroyed the interwall between the vascular channels. As illustrated in Figure S2, two metaxylem channels merged into a single one as also confirmed by the SEM image in Figure 4. It is important to mention that the pixel size resolution of images in Figure 3 is about 9 μm; therefore, objects smaller than this value are not observable by this technique. Consequently, the Cu-LμR was sliced and analyzed by SEM and EDS techniques (Figure 4). The distribution of copper deposited on the internal surface of the Cu-LμR channels was first observed with the optical microscope (Figure 4A). The optical images of transversal and longitudinal sections of Cu-LμR showed two inner brighter straight channels. One of them (diameter ca. 417 μm) was analyzed by SEM (Figure 4B) and corresponded to the fused metaxylem channels as previously observed by μCT analysis. The presence of Cu(II) inside the channel (and not in the outer space) was confirmed by EDS analysis (inset of Figure 4B). The EDS map analysis of the parenchyma tissue confirmed a high content of carbon and oxygen atoms and a very low presence of copper. By contrast, the concentrated amount of copper within the channel could cover the signals of carbon and oxygen atoms (Figure 4C−E).

Figure 2. FT-IR-ATR spectra for sliced (A) LμR, (B) LμR oxidized with TEMPO, and (C) Cu-LμR.

complexation with CuSO4 (Cu-LμR). The FT-IR spectrum of LμR showed adsorption bands characteristic of cellulose and hemicellulose (Figure 2A), centered at 3340 and 2981 cm−1, which were attributed to the −OH and glucose C−H stretches, respectively. The peaks at 1460 and 1376 cm−1 correspond to the asymmetric and symmetrical bending vibrations of C−H, respectively.34 The C−O−C vibration of the glycosidic bond appears as a strong band at 1059 cm−1. A small peak accentuated at 898 cm−1 is related to the C1−H deformation of the 1,4-β-glycosidic bonds of holocellulose.35 FT-IR of LμR after oxidation (Figure 2B) showed the formation of two new peaks at 1602 and 1406 cm−1 corresponding to the symmetrical and asymmetric stretching vibrations of sodium carboxylate (−COO−Na), as reported in the literature.31,36−38 This result indicates that the C6−OH carbons of holocellulose were successfully oxidized to carboxylate groups. Figure 2C shows the FT-IR spectrum of Cu-LμR, with the displacement of the asymmetric stretching vibration of sodium carboxylate from 1602 to 1593 cm−1, resulting from the interaction −COO−Cu(II).30,31 This is probably caused by the effect of the coordination of Cu(II) with oxidized holocellulose C


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Figure 3. (A, B) μCT images of Cu-LμR: transversal and longitudinal cross-sections of bamboo culm. (C, D) Three-dimensional image with and without the vegetal biomass. Dotted circular yellow line with internal diameter of 4.2 mm corresponds to the internal area of flow injection. Insight of the metal depositions onto microchannels (metaxylem, phloem, protoxylem) is highlighted with red lines.

Figure 4. (A) Optical image< (B) SEM image, and (C, D) EDS map spectroscopy of a longitudinal section of Cu-LμB vascular bundles. SEM image shows a fused channel with a diameter approximately of 417 μm. EDS maps identify the distribution of C, O, and Cu outside and inside the walls of the channel.

Click Chemistry with Cu-LμR. In our proof-of-concept study, the continuous-flow CuAAC was selected as the benchmark to test the effectiveness of the fabricated bamboo-based microreactors. A preliminary batch experiment was performed with a slice (ca. 1 cm2) of Cu-LμR using phenylacetylene 1a (0.14 mmol), 1-azido-4-bromobenzene 2a (0.12 mmol), sodium ascorbate (10 mol %), and water as the reaction mixture (Table 2, entry 1). Precipitation of the target adduct 3aa on the bamboo surface suggested the utilization of a MeOH−H2O mixture for the subsequent flow experiments to avoid clogging of the microreactor channels. Hence, 3 mL of a 2:1 MeOH−H2O solution containing the above reactants was initially circulated (peristaltic pump) through the Cu-LμR

Overall, these results indicate that functionalization of the polymer matrix with copper occurred preferably inside the channels with a small propagation of copper ions outside the vascular channels. According to the above analyses, the main features of the fabricated Cu-LμR can be summarized as reported in Table 1. These include the external dimensions of the reactor, the number of vessel elements and channels within the reactor, the internal diameter of channels, the geometrical volume, and the loaded amount of copper. The inner microchannel diameter seems to be quite irregular, but as we will show in the next section, this irregular vascular bundle organization does not influence the performance of the bamboo-based microreactors. D


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the reaction mixture was circulated for an additional 6 h affording 3aa in 80% isolated yields (Figure 5). This result

Table 1. Main Features of Cu-LμR Cu-LμR Fabrication Parameters external dimensions

o.d. = 6 mm; i.d. = 4.20 mm; h = 30 mm 8

number of vascular bundle elementsa (metaxylem + phloem + protoxylem) number of main metaxylem channelsa 16 mean diameters and area of metaxylem 151 ± 34 μm channelsa (min = 94 μm, max = 215 μm), 0.0193 ± 0.0081 mm2 mean diameters and area of 53 ± 19 μm protoxylema (min = 12 μm, max = 76 μm), 0.0028 ± 0.0010 mm2 mean area of phloema 0.0285 ± 0.0086 mm2 geometric volume VG of vascular 1.5 mm3 bundles elementsa Cu(II) loadingb 0.610 ± 0.063 mg, 9.6 μmol

2D and 3D μCT images have been analyzed by Dragonfly and ImageJ software.41 The main features of the vascular bundles from internode 7 are kept constant along the 30 cm length. bDetermined by ICP-MS. a

Table 2. Optimization of Continuous-Flow CuAAC with Cu-LμRa

entry

reaction time (h)

flow rate (mL min−1)

3aab (%)

residence timec (s)

1d 2 3 4 5 6 7

6 2 4 6 8 8 8

0.1 0.1 0.1 0.1 0.5 0.8

27 45 66 80 68 55

14.74 14.74 14.74 14.74 3.82 2.15

Figure 5. Evaluation of the contribution of homogeneous catalysis (leached copper) to the reaction outcome of the optimized flow process with Cu-LμR (entry 5, Table 1).

indicates that the leached copper ions contributed to a minimal extent to the catalytic process, which almost exclusively proceeded under heterogeneous conditions. As it was noted, the amount of copper detected in the reaction mixture was much lower than the concentration allowed in pharmaceutical compounds (15 ppm).42 Afterward, the reusability of Cu-LμR was tested by repeated experiments performed under the optimized conditions using fresh solutions of reactants after each cycle (Figure 6). A

a

1a (0.14 mmol), 2a (0.12 mmol), sodium ascorbate (10 mol %), 2:1 MeOH−H2O (3 mL), Cu/aryl azide molar ratio 0.08 (8 mmol %). b Isolated yield. cDetermined experimentally with LμR dry. dReaction performed under batch conditions in pure H2O.

at increasing times with a flow rate of 0.1 mL min−1 (entries 2−5). The optimal result was observed after 8 h (80% isolated yield of 3aa, entry 5), while a further increase of the reaction time did not significantly improve the reaction outcome. As expected, the process productivity diminished with the increase of the flow rate (up to 0.8 mL min−1) at the same reaction time (8 h), thus indicating saturation of the catalytic activity of CuLμR (entries 6 and 7). A small amount of copper (4.83 ppm) was detected by ICPMS in the reaction mixture of the optimized entry 5; therefore a subsequent experiment was aimed at evaluating the contribution of a homogeneous catalysis to the formation of 3aa. Accordingly, the reaction mixture was circulated through Cu-LμR for 2 h, and a product yield of 16% was detected by 1 H NMR analysis (Figure S3). Then, the pump was stopped, and the reaction mixture was stirred without contact with CuLμR for 6 h observing an increase of yield of ca. 2%. Finally,

Figure 6. Reusability of Cu-LμR and quantification of leached copper (ICP-MS analysis).

progressive loss of activity was detected in the first four cycles (3aa: from 80% to 73%) accompanied by a diminished leaching of copper ions (from 4.83 to 0.02 ppm, Table S2). Satisfyingly, a maintenance of process efficiency was observed in the fifth cycle (73%), thus demonstrating the synthetic potential of the novel copper-functionalized lignocellulosic microreactors for long-term operation. E



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Finally, the scope of the disclosed flow CuAAC procedure was extended to different substrate combinations, and it was observed that the presence of electron-withdrawing or electron-donating groups in the phenyl ring of the azide 2 did not greatly affect the efficiency of the coupling process (Table 3).

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Alessandro Massi: 0000-0001-8303-5441 Omar Ginoble Pandoli: 0000-0002-2220-7817

Table 3. Scope of the CuAAC Flow Procedure with CuLμRa

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors are grateful for the financial support from the Serrapilheira Institute (Grant Serra-1709-17482) and Coń selho Nacional de Desenvolvimento Cientifico e TecnologicoBrasil (CNPq) (458302/2013-9) and Coordenação de ́ Aperfeiçoamento de Pessoal de Nivel SuperiorBrasil (CAPES)Finance Code 001. O.P. thanks FAPERJ-Brazil for the JCNE fellowship (E-26/203.281/2016). Ph.D. student D.S.d.S., Post-Doc E.J.R.R., and undergraduate students R.B. and C.E.R.R. are grateful to CNPq for scholar fellowships. We thank Prof. Tatiana D. Saint’Pierre and Rafael Rocha for the assistance during the ICP-MS analysis. The collaboration of ́ and Prof. Sidney Paciornik with μCT Marcos H.D.P. Mauricio experiments is greatly appreciated.

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a

1a (0.14 mmol), 2 (0.12 mmol), sodium ascorbate (10 mol %), 2:1 MeOH−H2O (3 mL). bIsolated Yield.

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CONCLUSIONS In this proof-of-concept study, the fast and easy prototyping of a copper-functionalized lignocellulosic microreactor (Cu-LμR) from bamboo internode has been exploited to perform coppercatalyzed click chemistry reactions. It was possible to demonstrate the use of a natural template for the fabrication of microreactors by a low-cost process. The rapid prototyping LμR is suitable to supply a high number of microreactors necessary to setup a parallelized system for increased reaction output. The present environmental microfluidic technology allows a low-cost manufacturing with a better competitive scalability production of a new bio-microfluidic device to break through the established market of microfabrication technique. The disclosed method of bamboo matrix functionalization is currently under investigation for the immobilization of other metal or (bio)organic catalysts, thus paving the way for an alternative valorization of the abundant bamboo biomass in the field of microreactor technology.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b05273. Experimental conditions of reactions, μCT operational parameters, ICP-MS data, μCT setup, backpressure of LμR at different flow rates, 1H and 13C-RMN spectra of the CuAAC reaction products, and evaluation of the contribution of homogeneous catalysis (PDF) Tutorial video for the fabrication process of LμR (AVI) F


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