Spin-Controlled Helical Quantum Sieve Chiral Spectrometer

) chiral selectivity by a chirality-induced-spin mechanism that polarizes the local electronic band-structure in graphene through chiral-activated Rashba spin–orbit interaction field. Combining the MSSA structures with decision-making principles based on neuromorphic artificial intelligence shows fast, portable, and wearable spectrometry for the detection and classification of pure and a mixture of chiral molecules, such as butanol (S and R), limonene (S and R), and xylene isomers, with 95–98% accuracy. These results can have a broad impact where the MSSA approach is central as a precautionary risk assessment against potential hazards impacting human health and the environment due to chiral molecules; furthermore, it acts as a dynamic monitoring tool of all parts of the chiral molecule life cycles.


DOI: 10.1002/adma.202209125
mirror image structures known as enan tiomers. Chiral molecules have identical physical and chemical properties when present in an achiral environment. [2] Due to their essential role in various chemical and biological processes, the determina tion of absolute configuration and enan tiopurity is crucially important in a whole range of fields, such as biosensing, optics, electronics, photonics, catalysis, nano technology, and drug and DNA delivery; notably it is crucially important in drug production and the material sciences. [3] Several approaches have made signi ficant progress over the last few years for chiral detection methods. [4][5][6][7][8][9][10] These include chromatographic separation, optical polari zation, and sieving techniques, such as, supercritical fluid chromatography using a polysaccharidebased stationaryphase, optoelectronicsbased polarizer instru ments (e.g., circular dichroism spectro scopy), and a porous organic cage. [4][5][6][7][8][9][10] However, these instruments are bulky, expensive, powerhungry, need tedious fabrication and production methods, and require long processing time with stringent analyses by trained people.
At the front of the aforementioned challenges, sensors with various transduction mechanisms (e.g., chemiresistor, photo conductive, and field effect transistors) have been proposed for rapid, continuous, automated, and/or onsite precautionary risk assessments for potential chiral hazards impacting human health and the environment, and/or for the dynamic monitoring of all parts of the chiral molecule lifecycles. [11][12][13][14][15][16] Amongst the reported sensing approaches, enantioselective chemical microsensors based on helical structures, such as DNA, have also been pro posed for investigating extraterrestrial homochirality in space. [17] For these structures, efficient sensing performance relies on the energetically favorable binding of a specific enantiomer type to the helical structure through twopoint or threepoint inter action; at the time the other enantiomer has less favorable binding energy on the same helical structure. While good per formances have been reported with this approach, this strategy is not so effective in evaluating chiral mixtures because in most of the cases, the sensor device provides a superposed signal from a chiral mixture and lacks chiral separation. [11,14] Indeed, for the detection and classification of chiral mixture combinations, the use of these superimposed signals requires tiresome training of an uncountable combination of sensing signals. [18] To monitor the life cycle of each chiral molecule and pinpoint potential new chemical threats, it is first necessary to detect and This article reports on a molecular-spin-sensitive-antenna (MSSA) that is based on stacked layers of organically functionalized graphene on a fibrous helical cellulose network for carrying out spatiotemporal identification of chiral enantiomers. The MSSA structures combine three complementary features: (i) chiral separation via a helical quantum sieve for chiral trapping, (ii) chiral recognition by a synthetically implanted spin-sensitive center in a graphitic lattice; and (iii) chiral selectivity by a chirality-induced-spin mechanism that polarizes the local electronic band-structure in graphene through chiral-activated Rashba spin-orbit interaction field. Combining the MSSA structures with decision-making principles based on neuromorphic artificial intelligence shows fast, portable, and wearable spectrometry for the detection and classification of pure and a mixture of chiral molecules, such as butanol (S and R), limonene (S and R), and xylene isomers, with 95-98% accuracy. These results can have a broad impact where the MSSA approach is central as a precautionary risk assessment against potential hazards impacting human health and the environment due to chiral molecules; furthermore, it acts as a dynamic monitoring tool of all parts of the chiral molecule life cycles.

Introduction
Chirality is a property of molecules that results in their mirror images being nonsuperimposable, even with any translation or rotation. [1] This property arise when a molecule has an asym metric carbon atom or other chiral center, which creates two identify ideally all, or at least most, chiral compounds within the targeted environment or mixture. An ideal chiral sensor that could achieve this target demands four complementary characteristics: (i) it can strongly interact with chiral molecules so that it can detect the analytes at low concentrations; (ii) energetically favorable binding can induce strong responses and differentiate a pair of enantiomers with high sensitivity; (iii) the chirality induction is realtime and can be measured directly without aftertreatment; and (iv) the molecular host is easier to synthesize and chemically modify. One approach that could achieve these characteristics relies on advanced materials and geometrical structures that have the ability of producing opposite spin information from each chiral handedness. This property is commonly known as chiralityinduced spin selec tivity (CISS) [19,20] which could be practically initiated as an asymmetric electronscattering process in a chiral potential, dependent on spin−orbit interactions (SOI). [21][22][23][24][25] Essentially, spin adds new degrees of freedom for the conventional sensing approach. Its manifestation as a major recognizing factor for a chiral molecule to be established as a prominent transduction principle remains to be achieved.
We report here on the design and demonstration of a chiral spectrometer that can simultaneously separate and detect vapor mixtures of enantiomers. The detection ability of this chiral spectrometer is based on the chiralityassisted spincontrol prin ciple using spinsensitive and spinselective hybrid graphene pixels printed on a helical quantum sieve (HQS)based cellu lose structure with a cascaded architecture. By engineering a cascade of porous and hairy HQS networks as a Chiral Stationary Phases (CSP), it is possible to obtain the separa tion for mixtures of chiral molecules, through a spatiotem poral effect that binds and releases the chiral handedness of the molecules in diverse times and places. This detection and classification mechanism is examined and supported by: (i) molecular modeling for calculating the binding energy of the various components of paper (such as cellulose) with the enan tiomers and isomers as well as the asymmetry in energy and relapsing time for each component in the targeted chiral mix ture; and (ii) quantum mechanical study with density functional theory (DFT) calculation for evaluating the energy of inter action of chiral moleculeorganic ligands of sensor and spin influence on band structure. For application purposes, a neuromorphic visioninspired imageprocessing technique along with a deep neural network base is used to assess pure and mixture of target enantiomers/isomers qualitatively and quantitatively. Figure 1a presents the overall design structure of the spatiotem poralbased chiral spectrometer, which relies on chiral sensitive electronic architecture on helical quantum sieve (CSEAHQS) in cascaded layers. Each layer within the CSEAHQS consists of a variety of spinsensitive detectors (SSDs) that are made of different molecularspinsensitiveantenna (MSSA) receptors (chiral/achiral) grafted on to a graphite plane (see Section S1, Supporting Information) and operated by CISS. Thus, CISS pumped electrons polarize the conductive graphitic framework to certain spin states via MSSA, and such adatom creates Rashba, a SOI field as their presence breaks the space inver sion symmetry. [22][23][24][25] Due to the presence of multiple SSDs in each layer of the CSEAHQS, a splitting phenomenon for each SSD could be viewed simultaneously and in a multiplexed manner, providing classification/quantification of individual or mixture of chiral molecules using synthetic image processing (see below). The inset of Figure 1a shows the magnified schematic of the printed SSD on helical cellulose like fiber structures (HQS). While the measured sensing signal in the top cascade layer is a superimposition of both types of chiral molecules, it is likely that signal from second cascade layer will show a spatio temporal chiral separation (resolving power) due to helical interaction of cellulose and each enantiomers). Figure 1a[i-vi] shows the schematics of the channel polariza tion from the enantiomer's spin injection via the implanted scattering center, expressed via a dopamine ligand that is chemically attached to the graphite surface. Also shown is the unpolarized electron injected from the lead to the channel to gain more uniform polarizability due to the implanted scattering center while passing through the Rashba region-a region that is influenced by a certain spin state as destined by type of the chiral molecule as well as the efficiency/quality of spin transfer through the ligands. The advantage of weak spinorbit and hyperfine interactions in the organic ligands helps in preserving spincoherence over time and distance, which are much longer (≈13-110 nm) than conventional metals. [26][27][28][29] As such, tuning the grafted organic ligands on the graphite plane of the MSSA can act either as a coherent spin channel or as a spin filter.

Design of Chiral Sensitive Electronic Architecture on Helical Quantum Sieve
A special spin polarization originating from certain chiral molecules can be transported through organic linkers to a graphitebased channel. Depending on the handedness, this can cause opposing change in resistance. This capability to dis tinguish different spin directions, known as 'spin filter', results in a specific spin type being accepted while the other spin is not. In the "spin filter" case, specific spin (viz. up) is selectively transferred to the channel and remains opaque for the other spin type (viz. down). The result is chiral selectivity expressed by a change in the resistance (increase/decrease) for one specific enantiomer and silence for its mirror type (see Figure 1a[i-vi]). Relevant to this case is the adatom of the organic ligand implanted on the graphite lattice that act as a scattering source for precessing the incoming electron spin, as per Rashba field direction (Dyakonov-Perel type) or local magnetic moment influence (resonant scattering type) -see Figure 1b,c. On expo sure to enantiomeric vapor molecules, these scattering regions indicate the same direction of the Rashba field and magnetic moment throughout the entire exposed area of SSD, creating a strong spin polarization effect from local counterpoints to glob ally across the SSD. This effect is termed throughout this article as "chiral activated Rashba effect" (CARE).
The Rashba SOI effect is empowered when a scattering center is spinpolarized by the chiral environment (CARE phenomena) and a spinpolarized band gap is modulated in the presence of such heavier dopant that radically changes the local electronic structure (see Figure 1b,c). In the presence of electric field in the same direction, where inversion symmetry is broken, E (= E z ), a moving electron with a velocity v experiences a relativistic effective magnetic field B. Therefore, Zeeman influence on the electron takes the form of the Rashba SOI, as expressed by: Adv. Mater. 2023, 35, 2209125 Figure 1. Spin-controlled chiral spectrometer using the relativistic chiral Rashba effect, MSSA, and HQS as chiral stationary phase. a) CSEAHQS architecture based on chiral spin spectrometer with embedded signal processing unit and deep net-based decision-making system using synthetic image processing from the feedback of SSDs. The arrows (up-down, up, down, and no symbol) signify the operating mode of the detectors that can sense up and down, up, down, and no spin type, respectively, depending on the functionalization status around the graphite plane. The HQS structure is shown in the dotted inset. The Rashba SOI region and CISS-based spin transfer from chiral molecules adsorb on such MSSA is shown for polarization of the channel and compared with various cases, such as (i) without enantiomers vapor (negligible polarization), with enantiomer, for (ii) spin-up, and (iii) the spin-down polarization case, where MSSA transfers both spin-type coherently. MSSA is tuned for spin filter to allow (iv) specific spin (such as up) that detect specific enantiomer by polarizing the channel selectively, and (v,vi) opaque for other spin types (defined as "x") that have negligible influence in channel polarization and have an insignificant resistance change that leads to chiral selectivity. b) Relativistic representation of moving spinning electron and polarization by SOI is considered in the observer's moving/rest frame of reference for the direction of moving electrons (v), electric (E y ), and magnetic field (B z ). c) Schematic comparison of two cases showing chiral Rashba SOI for polarization of electron flow without (left) and with (right) enantiomer in a 2D SSD system.
where α z = (ℏ/mc) 2 eE/2 gives the Rashba energy scale and σ and k are electron's spin and crystal momentum, respectively (see details in Section S2, Supporting Information). This arises from the inherent magnetic field due to a relativistic effect, which is the key factor for spin polarization without an external field. This relativistic effect is advantageous over other magnetic resonance spectroscopy, such as electron spin reso nance (ESR) and nuclear magnetic resonance (NMR), where an external magnetic field is needed to generate the electron spin energy band splitting and the radio frequency scanning to iden tify them.

Synthesis and Printing SSDs on HQS
Printing the SSDs is carried out by the binderfree inkjet technique using dopamineassisted reduction of graphene oxide (GO) functionalized with molecular spin sensitive antenna, expressed by various chiral and achiral biochemical ligands (see Figure S1 and Section S1, Supporting Information). The advantage of the implemented binderfree printing technique is that it does not need any postprinting annealing, making it suitable for highquality printing on wide range flexible/rigid and porous substrates (e.g., paper, Kapton, glass, PDMS polymers, and PET)-see Figure 2a-j. Figure 2k shows typical scanning electron microscopy (SEM) of reduced GO (rGO) nanoflex after reduction. The details of the chiral/achiral biochemical ligand are given in Figure S1, Supporting Information. The functionalizedrGO inks are printed in a multijunction array electrode on a porous paper substrate that acts as HQS. Figure 2l shows an optical image of a representative CSEAHQS, in which the 20 black pixels represent various functionalizedrGO detectors and the gray lines represent the silver nanowirebased electrodes and connectors. Figure 2m shows the Raman spectroscopy meas urement and the calculated I D /I G ratio for GO, rGO, and various functionalized (chiral/achiral) rGO. The increase of the I D /I G ratio after reduction suggests it is an effective reduction procedure. Figure 2n shows a Fourier Transform Infrared (FTIR) spectrum. The higher intensity shown near the 1000-1100 cm −1 region suggests effective chiral/achiral ligand based loading on the graphite plane. Figure 2o presents a comparison between the NMR spectrums of rGO and various functionalizedrGO inks. A new peak at ≈2.75 ppm is detected, suggesting effective functionalization status of each. Figures  2p and 2q show, respectively, basic field effect transistor (FET) transfer curves and current-voltage (I-V) measurements for rGO sample I-V measurements. The results indicate for ntype FET with Ohmic contact, most probably due to the N 2 doping made by the polymer chain of the polydopamine scattering center. Additional information regarding NMR is shown in Supporting Information ( Figure S2, Supporting Information).
Figure 2r-w and Figure S3, Supporting Information, show the biocompatibility results of rGOs with various chiral/achiral ligands, which are for the cytotoxic assessment of untreated human lung epithelial cells (BEAS2B, ATCC, and CRL9609) after 10-100 µg mL −1 treatment for 24 h. The viable cell per centage after treatment has been compared with untreated cells (Figure 2x). Functionalized rGO inks had negligible cytotoxicity both at low and high concentrations. This assessment could be useful for a continuous production line during fabrication, printing, and measurements regarding par safety issues (see details in Section S3, Supporting Information). The photo graphs of largescale printing on paper, porous, and fibrous cel lulose from paper substrate are shown in the Figure S4, Sup porting Information.

Simultaneous Separation and Recognition of Chiral Molecules
A schematic representation of spatiotemporal separation of chiral molecules using the cellulosebased fibrous and porous cascaded HQS is shown in Figure 3a[i]. Due to the pres ence of an inherent chiral center and the helical shape in the HQS, the incoming enantiomers ((S) (+)2butanol and (R) (−)2butanol)) reach the second layer of the CSEAHQS in a lagging manner and react with the SSD at different time frames. This causes a divided electrical resistance profile that depends on the nature of spin sensitive/filtering capability as well as various splitting (abundance) profiles of each enantiomer in the mixture from Layer 2; at the time, a super imposed Gaussianlike profile is observed from Layer 1. The specific binding time and release of each handedness from such CSEAHQS at different times from t 0 to t 3 is schematically shown in Figure 3a[i,ii]. Figure 3b-e shows the response pattern to (S) (+)2butanol and (R) (−)2butanol, either as individual components of mixtures with racemic (1:1) and enantiomeric (2:1 and 1:2) ratios, from Layer 2 of the CSEAHQS for different SSDs with typical achiral ligands (e.g., 4mercaptobenzoic acid (MBZA), 1,4Phenylenediamine, and diethylamine) and chiral ligands (e.g., 3mercapto hexanol). SSD with the MBZA shows complete opposite behavior for two different chiral handedness, viz. increase of resistance (up) for S (+) and decrease of resist ance (down) for R (−). When compared with the same SSD type (MBZA) in Layer 1 cascade, the sensing profile looks single Gaussian type with no resolving power (see Figure S5, Supporting Information). The other SSDs had either opposite directions or the same directions for individual chiral handed ness. Typical data are shown for various cases as per direction ality, such as, down-down (1,4Phenylenediamine in Figure 3c), down-up (diethylamine in Figure 3d), and up-up (3mercapto hexanol) with related splitting results in the mixture. Each of the splitting profiles is distinct from each other with the presence of a multipeak, suggesting the relative abundance in different timeframes as per transmission rate of each chiral type from Layer 1 to Layer 2, meaning that Layer 2 of the CSEAHQS is more informative than Layer 1 in a racemic/ enantiomeric chiral mixture.
To understand the opposite directional changes in chiral S (+)/R (−) exposure, ab initio DFT analyses were conducted for typical SSD case (up-down, Figure 3b   . Uniform continuous printed geometrical pattern (typical square and rectangular pattern ≈3 × 3 mm 2 and ≈3 × 4 mm 2 ) on various rigid and flexible substrates, such as c) Kapton, d) silicone PDMS rubber, e) glass, f) PET, g) filter paper, and h) conventional office printer paper. Magnified image for continuous printed pattern with no "coffee ring effect" on the edge for i) silicon and j) Kapton. k) The SEM microstructure of rGO nano-flex and l) the typical photograph of CSEAHQS with SSD pixels printed on paper. m) Raman, n) FTIR, and o) NMR characteristics of SSD inks. p,q) FET and IV characteristics of rGO. Evaluation of cytotoxicity using human epithelial lung cells (r, untreated) for various SSD inks (thiol, amines, and chiral), such as mercapto hexanol (s (i, ii)), mercapto benzoic acid (t (i, ii)), diethanolamine (u (i, ii)), diethylamine (v (i, ii)), 2-amino-4-chlorobenzoic acid (w (i, ii)) at (i) 10 µg mL −1 and (ii) 100 µg mL −1 dosages, respectively (24 h).
x) The live cell percentages for various functionalized-rGO ink concentrations and types of dosage after 24 h treatment.
host-guest complex (for Shost and Rhost) is calculated as 0.273 and 0.276 eV, respectively, and is lower than that of the host (≈0.281 eV) for both cases. Mullikan charge analyses show that chiral VOC fragments of S (+)/R (−) butanol MBZA PDPrGO complexes are positive in values, such as, 0.0117 and 0.0137, respectively. This signifies that the butanol fragment for each enantiomer case contributes the charge to the host SSD, suggesting decreased resistance for each case (same direc tion). However, that contradicts the real observation of SSD measurements, which has an opposite directional change of electrical resistance.
Pure graphene consisting only of carbon atoms arranged in a hexagonal lattice, is diamagnetic and does not exhibit magnetic behavior. However, when foreign atoms (such as,  H 2 , N 2 , F) or defects are introduced into the lattice, they break the symmetry of the materials. This phenomenon causes the overlap of pelectron orbitals and creates a magnetic moment in the crystal structure. [30][31][32][33][34][35] (This is highly desirable for spin tronics and chiral recognition. In general, during chiralbased charge transfer, the interaction is also accompanied by spin injection, which is completely opposite to each enantiomer type (CISS). Using this unique spin population, a graphite plane changes markedly its electronic properties (see Figure 1b). This could be attributed to the breaking of local symmetry by Ndoping in the CC lattice during polydopamine encapsu lation and reduction of GO to ntype rGO (see schematics in Figure S1, Supporting Information, and ntype FET properties (Figure 2p,q)). The presence of such a scattering center in the 2D lattice in the presence of a specific chiral environment polar izes the channel to a specific spinstate by the Rashba SOI effect and this should be electronically different without the enanti omer (see Figure 2p,q). It will also be different for a different chiral type. The presence of such N 2 scattering center in the 2D lattice in presence of a specific chiral environment polarizes the channel to a specific spin state. This should be electronically different without enantiomers (see Figure 2p,q) and should be opposite for different enantiomer types. To see this effect, DFT bandstructure calculation using opposite spin population (<↑| or <↓|) on N 2 incorporated graphene was done. Figure 3i shows distinct band modulation plot for each type (blue: spin up [E g = 0.085 eV] and red: spin down [E g = 0.069 eV]). This opposite band adjustments due to CISSassisted opposite spin population could be the reason for reverse resistance changes for each chiral handedness.
MSSA receivers on the graphitic lattice could also act as a coherent spin channel, so that specific spin from the enanti omer could reach to the graphitic lattice without losing primary spin information. These results are in alignment with previous theoretical and experimental studies that showed the ability of various ligands (e.g., thiol [SH], thiolates [S], amidine [NH 2 ], and carboxylicacids [−COOH]) to serve as frontier orbitals with larger spin relaxation length due to small SOI even at room temperature. [36][37][38] Other studies have shown that ferromagnetic lead (spin injector) coupled with such organic linkers (spin channel/filter) indicate coherent spin transmis sion capability. [39] This fascinating result seems highly practical in our case; yet, instead of using a ferromagnet, the spin injec tion source consists of chiral molecules in one end, while their relative effect is felt at the other end of the functional ized graphite lattice. Figure 3j-l shows such selective chiral response for various other SSDs with different ligand types. The schematic representation for a specific chiral filter type is shown in Figure 3m. One similarity for these three cases is that each of the ligand types has two consecutive benzene rings in their structure.
To evaluate the chirality resolving power of CSP through splitting resistance profile of enantiomeric mixture, molecular modeling simulation was used to show the binding affinity between cellulose and each vapor type of an enantiomer with defined chiral center. The calculated energies for cellu loseS (+) butanol and celluloseR (−) butanol complex were −146 113.24 and −146 112.25 kcal mol −1 , respectively, suggesting an asymmetry in the binding energy that cause difference in the releasing time for each enantiomer type while passing through hairy fibrous network (from first layer to second). The experimental evidence for the separation capability of helical cellulose fibers for different enantiomers has been reported elsewhere. [40] The typical separation factor, retention factor, and resolution for racemic mixtures of S (+) butanol and R (−) butanol are shown in Figure S6, Supporting Information, using typical ligand 1,4Phenylenediamine as a SSD concerning the direction resistance change of each enantiomer type. The fit ting results to evaluate such parameters for opposite directional resistance movement of current in chiral exposure for other ligands are problematic due to overlap issues. To counteract this issue, and for automated estimation of the components of chiral molecules in the mixture, a synthetic imagebased clas sification was carried out based on such splitting responses of all SSD types and deep learningbased model for automated classifications and quantifications of different chiral mixtures (see Section 2.3).

Neuromorphic Vision Synthetic Imaging of Spin-Pumping to SSD Receptors
To extract the automated features and for continuous estima tion of each chiral type in the mixture automatically from such a splitted resistance profile from each SSD, a synthetic image processing technique and a deep neural networkbased self learning architecture was tested.
Layer 2 of CSEAHQSbased SSD detectors was used to construct synthetic image profile for pure enantiomers and their mixture via a bioinspired neuromorphic human vision (Figure 4a) and neuromorphic spintronics. [41,42] Figure 4b-f shows a typical image quality as seen by the combined influ ence from each SSD. The images show distinct patterns bearing the influence of MSSA chemistry, interSSD dependence, and spatiotemporal splitting information by HQS in one image (see demonstration Videos S1 and S2, Supporting Informa tion). These composite images were then used for a deepnet system for selflearning architecture as input, with systematic training and the relative chiral concentration ratio being evalu ated with color coding (Figure 4g) for a realtime view for indus trial production line and classification accuracy (>95%) shown in a confusion matrix with relevant color coding (Figure 4h). Figure 4k shows the photograph of a chiral microspectrom eter embedded with a microprocessorbased computing unit, bilayer printed SSDs, and inlet/outlet. The reported CSEAHQS system was also tested upon expo sure to other chiral enantiomer vapors, such as limonene (+ and −) and their mixtures (racemic and enantiomeric). The difference between the two enantiomers of limonene (Slimonene and Rlimonene) as supplied is their chiral hand edness with distinct properties, such as a completely dif ferent smell. Enantiomer (R) has the characteristic smell of oranges, whereas the (S) smells like lemons. The SSD gener ated image patterns for pure (1:0 and 0:1) and mixtures (2:1, 1:1, 1:2) of these enantiomers are shown in Figure S7a-e, Sup porting Information, and are unique in each case. The calcu lated energy of celluloseSlimonene and celluloseRlimonene was −158 107.92 and −158 081 kcal mol −1 , respectively. This represents asymmetry in a binding energy with HQS while forming the complex during their passage from one layer to next. The optimized geometries of each complex are shown in Figure S7f,g, Supporting Information.

Sensing Study of Mixed Isomers
The present system was also tested for isomer sensing of xylene (ortho, meta, para) for pure samples and various mixtures of them (o:m:p = 1:1:1, 2:1:1, 1:2:1, 1:1:2). The typical image pattern is shown in Section S8 and Figure S8a-h, Supporting Information. The relevant classification result is shown in Figure S8i, Supporting Information. The figures indicate that the reported CSEAHQS could also be used for isomer sensing for individual and mixed samples. The major reason for the splitted sensing profile could be related to the asymmetry in the binding energy of isomers with the components of papers, for example, predominantly with cel lulose (see the optimized structures in Figure 5a). Other small amounts of components such as xylan and glucan could influence some amounts in mass transfer rate and isomeric elution as well (the optimized structures are shown in Figure 5b Table S1, Supporting Information.

Possible Applications of CARE Phenomena, MSSA, and CSEAHQS
As mentioned above, CARE phenomena express a polarized scattering when a chiral molecule is adsorbed on the SSD surface. In contrast to conventional unpolarized scatterers (e.g., hydrogen and heavy gas atoms adsorbed on 2D graphite lat tice), the CAREcontrolled spin modulation source can be used for maintaining longterm coherence. This could be attributed to the CISSpumped spin specificity and MSSAbased spin filtering when the surface is bombarded with chiral gas mole cules. In this configuration, chiral exposure could affect the entire channel with specific spin types, leading to an oppo site resistance change for two different enantiomers that are adsorbed on the specific SSD. In this context, it has to be clari fied whether the experimental demonstration of spin coher ence time is problematic, because the injected enantiomer molecules come, react, and leave the SSD (like a pulse) due to the continuous dynamic flow from one layer to another (HQS's hierarchical structures). Exposing the SSD to a constant chiral atmosphere could enable the efficient utilization of the CAREcontrolled organicinorganic CSEA hybrid approach. Another advantage of the CISSpowered CSEA hybrid device is that it does not necessarily need a third electrode (gatecontrol of spin) nor the ferromagnetic electrode (spin injection ports)/ high voltage, like the conventional spin transistor type, [43] as the implanted organic MSSA filters on graphite lattice can transfer a spin polarized electron to the channel. Conventional spin tronic devices need permanent ferromagnetic electrodes and are problematic for miniatured nanoscale spintronics because ferromagnetic materials behave superparamagnetically at nanodimensions. However, the present MSSAbased approach could be applicable for conventional nonmagnetic electrodes with no issue for miniaturization. Therefore, this could be highly useful for developing quantum electronics, lowpower magnet freespintronics, and fundamental device components of quantum computing at room temperature. Nevertheless, the reported cascaded architecture of the porous HQS sensing system could be utilized for other mixed gas sensing appli cations with a simultaneous separation and recognition, by increasing sensorprinted paper layers, paper quality, and thick ness of a specific paper grade. This will be highly important for drug research and molecular spectroscopybased clinical diagnosis of diseases of the skin, breath, blood, cancer tumor recognition, etc. [44,45]

Summary and Conclusions
We have reported on the design of a spincontrolled spectro meter using binderfree printed hybrid graphenebased SSDs, coupled with a cellulosebased helical sieving effect (HQS) in CSEAHQS architecture. The proposed system shows simulta neous chiral recognition and chiral separation of a variety of mixed chiral organic molecules, such as butanol (+ and −) and limonene (+ and −). Chiral recognition is achieved by CISS assisted spin injection from specific enantiomers and received through a MSSAbased implanted ligand on the graphite plane and CARE, which is generated by an effective magnetic field on the moving charge inside the 2D lattice through a relativistic effect. It proved advantageous to use a magnetfree approach for chiral spectroscopy compared to other magnetic resonancebased spectroscopy, such as NMR/ESR. Due to the small SOI and negligible hyperfine interaction specific ligands at some SSDs, chiral selectivity was found by allowing specific spintypes (spin filtering). Chiral separation was observed by the splitted resistance profile, caused by asymmetry in the binding energies between the HQS phase and enantiomers. This is highly useful for generating a unique synthetic image pattern and can be later used for estimation of chiral mixtures or isomer mixers with a neuromorphic vision inspired deep learning architecture. The proposed miniatured SSD spectrom eter design, along with an AI supported automated analyzing system, could be useful in the rapid detection of drugs, chiral spintronics, and other automated industrial process optimi zations. CARE phenomena and MSSAbased spin pumping/ filtering could be used for magnetfree nanoscale 2D spin tronics, a gatefree spincontrolled device, as well as room temperature spintronics and quantum computing.

Experimental Section
Binder-Free Inkjet Printing Recipe for Functionalized Graphene Ink: The dried functionalized hybrid rGO powders modified with a selection of chiral and achiral ligands was redispersed in DMF and sonicated at low power for ≈1-2 min to disperse the ink that was subsequently used for inkjet printing (Dispensing system with piezoelectric nozzle [Scienion, model sciFLEXARRAYER S3]) on paper for preparing the SSDs. Details of the synthesis, binder-free print approach, printing on a wide range of substrates, reaction mechanism, and list of biochemical ligands (thiols, amines, chiral compounds) are discussed in Section 1. The silver nanowires-based electrodes were used for connecting multi-SSDs. Details of the synthesis procedure is provided in Section 3.
Surface Characterizations: A morphological study using SEM (Sigma 500, Zeiss Ultra-Plus High-Resolution SEM, Germany) gave a microscopic view of the synthesized materials dispersed in alcohol and spin-coated on silicon wafers (Si/SiO 2 ) to distribute the flakes uniformly. Images were acquired at ≈5 kV electron acceleration and 4-8 mm working distances. Raman spectra (Horiba Jobin Yvon LabRAM HR Evolution Micro-Raman, Japan) were obtained with a 532 nm laser. All samples dispersed in ethanol were spin-coated on silicon wafers and dried overnight in a vacuum chamber before measurements were taken. For FTIR (Bruker Vertex 70 V KBr BS vertical ATR-FTIR, USA) measurements (300-4000 cm −1 ), the cleaned and overnight-dried sample powder was mixed with KBr to form a pellet. 1 H NMR analysis was done with a Bruker AV-III400 MHz 2-channel spectrometer with direct detection probe based with automatic tuning and matching (equipped with z gradients) at room temperature, using ≈500 µL d-DMSO (Sigma Aldrich, USA) as the solvent at 30 °C, a 1 H pulse with 1 s repetitions.
Cell Culture Treatment with Functionalized rGO Inks to Assess Cytotoxicity: Human epithelial lung cells (BEAS-2B, ATCC, CRL-9609, Israel) were seeded at 96 × 10 3 per well on 24-well plates and cultured with 0.5 mL full Roswell Park Memorial Institute (RPMI)-1640 medium (Sigma-Aldrich, Israel) at 37 °C with 5% CO 2 in air. After 24 h recovery, the cells were washed with phosphate buffered saline (PBS) Ca 2+/ Mg 2+ (Sigma-Aldrich, Israel) and the treatments were applied for 24 h in the culture medium. Hybrid rGO samples were cleaned with ethanol and dried overnight before cell culture. The typical hybrid rGO powder samples containing different thiol/amine-based chiral/achiral ligands, such as mercapto hexanol, mercapto benzoic acid, diethanolamine and diethylamine, and 2-amino-4-chloro-benzene thiol were vortexed with RPMI 1640 medium at 10 and 100 µg mL −1 . The cells were then exposed to each hybrid rGO sample from ≈10 to 100 µg mL −1 for 24 h. The experiment on an animal model using functionalized rGO could be found elsewhere. [48] Annexin V-FITC/Propidium Iodide Assay: After 24 h treatment at the indicated concentrations, cells were gently washed with PBS. Annexin-V and propidium iodide staining was used (BioLegend, California, US) at 0.2 mL RPMI-1640 medium per well. The cells were gently washed with PBS and 0.2 µg mL −1 Hoechst 33342 solution (Invitrogen by Thermo-Fisher Scientific, Israel) was added. The cells were analyzed using an In Cell Analyzer 2000 System (Technion Life Sciences and Engineering Infrastructure Center, Technion, Israel). For details, see Section S3, Supporting Information.
DFT and Molecular Modeling: Gaussian 16 software was used to optimize the molecular structure as well as the HOMO and LUMO energy of polydopamine-rGO, (g) S (+) butanol-polydopamine-rGO, and (h) R (−) butanol-polydopamine-rGO, and also their complexes R-and S-2-butanol molecules using a DFT method with Austin-Frisch-Petersson functional with dispersion (APFD) and the basis set 6-31G (d). APFD, including treatments of the dispersion effects, represented the best trade-off between accuracy and computational cost for a relatively large system. [49] After relaxing the geometry of the host (cellulose) and the target (enantiomer), a docking simulation (generally followed for protein-ligand binding calculation) was used for finding the lowest energy position to measure molecular dynamic simulation. The typical boundary of the simulation box was set as 45 × 45 × 45 Grid size with a resolution of 0.4 Å in a flexible mode. The maximum number of the host guest pose was set at 5000 to find the suitable position for binding. Ab initio quantum DFT analysis for electronic structure and spin-dependent band gap calculations was carried out for the iterative solution of the Kohn-Sham equation in a plane-wave set with ultrasoft pseudopotentials. Here the Perdew-Burke-Ernzerhof exchange-correlation functional of the generalized gradient approximation was used. The plane-wave cutoff for wave function was set at 597 eV. The graphene sheets were separated by ≈20 Å along a perpendicular direction to avoid interlayer influence. The Brillouin zone was sampled with the Monkhorst-Pack scheme with a 7x7x1 k-mesh in Gaussian smearing condition. Spin polarization involved replacing one carbon atom with N by setting the 100% spin up/ down configuration at the N site.