RELATED APPLIC ATION

|M·I| lib ^plicalio· dams priority benefit oeder 35 L.S.C § 119(e) of L.&. Protbwml Appficatom No 62/164 _^ 276 filed June 20.2019 die contents of which ere herein incorporated by

GOVERNMENT RIGHTS

|Wi2| This invention was male wtA govemmrot support via grant* ftom NSF. grant

*% 1727551. 172*1*1, 1752*46 and 1663367 and a gram from U S Navy OflSoe of Naval Rssaawh (NAVY.ONRk grant a N000M- 18- 1-2*56 The gmxmmcm has certain rights in ike

BACKGROUND OP THE DISCLOSURE t*M3| The ability to pattern material response. voxd-by-voxri, to direct acaiarion and manipulation in macroscopic snuemres can enable devices that uhlue ambient stimuli to produce liquid crvmliM pohrmm (I.CPX where Ae nolccslir i6meiw it. "mdeteMy defined m i- dimensional fiedbrms can be a key onahlei Here, die combination of anisotropic magnetic susceptdnhiy of die Squid crystalline monomers in a roonsnisble magncoc field and spatially· selective phompolyeieroabon uring a digital miaumirver device m indcpcadcndy define molecular orientation in light andw heal responsive nudtwnakrid d which ae addidvdy incorporated Into 3-dUnenaional fiwfgnsi if cxploiaad Thb is riwa to enable orucuna ⁾ complexity across length series m oon-tnvial geometries, indudiag reentrant shapes which ere rasponahe to either heal or light A range of monomer compositions are optimund to include phutuintiiators. Kghi absorbers and polymerization inhibitors to modulate the pdymerbahod characmristics. while sunritSMously retain ag tbs tadorshility of die ncmabc alignment The versaiilitv of this framework b illumed la an aiay nf examples, iedndmy I) dwamumeefcanieri gencratka of Gaussian cursed structures from flat geometries. *> light

1 responsrve freeform topoipaphics and na> multi responsive manipulators, which can he powered along independent axes wring bear and'or light

|M04| KliYVrORDS: «ten matensh. liquid crystal pdynnn. additive manufacturing. 4D printing, soft rohodex

Ibeesi United States Fates* Appiicauoo Puhhcabon Nv 20100077071 (the ^{* *} 071 hjMkatocm ^** ) puMished on March 14. 2019. entitled ‘‘F.xtrosioa Frinting of liquid Crystal Elastomers’" is incorporated by reference hescia for all purpoe*

|NM| As set fdith in die ‘071 PbbKcrtkm. four-deneneonal (4D> p« wiring is a term dm describe* additive manufacturing of stimull-rcsponsivc material*. I his process lesuitt in ¾D «nurtures capable of morphing into s distinct 3D geometry over lime These morphing structure* nw onMc a wide variety of smart device» from soft robots to morphing medical device» A variety of material siacpn have arisen to amble dww morphing structures. Primed shape memory polymers can he roedencally processed after fabrication to lamporanly store and then recover a pruned shape However, this method may impure mechanical programming to achieve desired shape change fo fabricate 3D structure» capable of autonomous and rrenuhle shape change, several strategic» have been developed dm program the stimulus response of the material during the printing process Important to this strategy is programming material ncrortruaurts is a way that control· macroscopic deformation* For example, by cootrolliag die local coefficient of thermal expansion in printed structures, porous objects with negative global coefficient of thermal expansion can be fahrieaied However, tins deformation ½ Bruited by dwr «nail magritude and isotropic desigmag morphing shucturcs is to locally program anisotropic stimulus response Direct-write priming (often refereed to as extrusion-printing herein), mi intrinsic aaisouopic proems on be used to cream hydrogels that locally swe* anisotropically. Ibis large, propammabk shape change cw be utiliaed to craale structure» that bend, twist, or curve on the macroscale However, shape change in hydrugds ½ often limited by diffusioe speed and the requisite aqueous environment h would be desirable to have printable material» diet undergo large, amsotnyic. rapid, and laversiMe deformations to enable future 4D primed smart »> item»

|M07| Liquid crystal dasiommfl CFs) are a date of sriamli-ittpooaive polymers that undergo huge, reversible «isotropic shape change is response to i variety of stimuli, including heal aad

- 2 - byN Urdilcc many mntcrialt dial eedergo icvatible shape change, these material* neither require an external lend nor an aqueoua envti applications for IX'Ks to undergo reversible dope-change m the abianoe of load. die IX>‘ should be aomlinked in aligned we Commonly. partially ciwinkd LTEt arc Asiy crotdinked under a mechanical load lending to permanent onentadon of die liquid crystal (LC) molecules within the polynw network On heating, the resulting aligned LCLs contract along the alignment direction, or nematic director, and «pend in the pcrperwSoiar axes With this process.

•I is difficult to program die stiraulut response of die material In a spatially-varied maanai As such, several methods have been developed to align monomeric or ohgomcric LCk precursors. Uriag patterned surface treesmcai* first developed to pattern densely crowlinled I G polymer networks IX ^* monomers can be patterned widi high spatial leaolutk* IXT.s rcwWnn from rids process can be designed to undergo hodi m ptaae and eut-of-planc patterned shape change

However. di¼ technique maybe limited to the production of rcLmvdy thiw. planar films (kss dun IOOmhi thick) Sbcm forces have been shown to induce alignment within atonomanc and oligomeric LC molecules Alignment results from proecama such as alectrospinmng and fiber drtwiag from the mdt However, to our knowledge, shear has not been used to spatially or hierarchically control alignment wiihro I XT* low density. large shape change, end autonomous activation provide critical benefits, including applications such m soft robots, artificial musdes. aansors and aerrapnee systems. These smart materials can be deigned to transduce thermal chemical. or light energy into

As oonipmed to rigid active materials, such as shape memory alloys, a primary advantage of acuvc soft materials is dial polymer processing technique* can be used to cuntiol the properties of the material A number of eonvuebonal manufacturing strategics have been roeendy. additive manufacturing techniques have been applied to medunically-eetivc polymers The roaddag primed. )D structures arc capable of undergoing change in shape over time and, as used to fabnottc a range of mechanically-activx smart materials, such as shape memmy pulymas (SMIS). hydrogdi. and fluadk elastomer actuators (PίAc) Demonsuated 41) primed structures indude SMP hinges in orijpmi robots, morphiiig hydrogel arudmek mad somaioicirstivc grippers with complex networks of I I A sensors I lowcvei . dll of these materials strategies have fundamental design limitations preventing them from achieving reversible. untcthcrodL and low-hysteresis shape cliange that would enable 41) printed materials to operate as autonomous morphing structures For example, printable SMPs exhibit irreversible deformation, limiting SMPs to applications requiring deployment Reversible swelling in printed, anisotropic hyxirogd composites can be used to create morphing structures but these materials have relatively low Mocking sue» and diffusion-limited actuation speed FkAs can exert high stresses but require a tethered fluid pressure system to induce large revet >i hie deformation

|6009] liquid crystal elastomers (IX'Ls) are mechanical !v-activc soft materials that undergo reversible sliapc change that <kxs not require mechanical bias, aqueous environment, or tethered power source and as such these materials are of inlet as actuators and morphing structures. Shape chance of up to 4 ⁽ X/ ¹ n is observed in response to stimuli that induce the transition of the material from ordered to disordered, most typically a change in temperature Finkdmann atxJ co- workers fust reported this behavior by uniaxially aligning LCEs during crosslinking by applying a load Recently, several processing methods have arisen to enable LCEs that undergo complex shape change in response to a stimulus I.i<|uid crystal elastomers with dynamic covalent bonds have been synthesized that can he aligned during bond rearrangement Furthermore chemistries amenable to surface alignment techniques have been introduced allowing for precise patterning of the nKiktular order m a voxel -bv voxel manner. LCEs produced by this method mmph ncvcrsiblv from planar films to complex shapes in response to an environmental stimulus Recently, our group and others have used direct ink writing (DIW) to print 3D I.CF geometries with patterned molecular order. The method utilizes the shear forces imposed on the polymerizable LC ink dunng the printing process to align the mesogens along the printed path, which is subsequently locket! into LCF via photocuring The resulting 3D structures can be designed to morph between 31) shapes However this method has been limited to LCEs with elevated actuation temperatures in excess of 100 ~V . which limits the functionality of this new processing technique for I.CF.s

10010) In LCEs the actuation temperature of the final material is minnsically tied to the processing conditions To orient precursors of the lCb. the precursors must be processed m a liquid crystalline phase <i e nematic phase) C'rossl inking convats these precursors into I.CFs with programmed molecular orientation but also stabilizes the nematic phase, thus increasing the

- 4 - temperature between the ordered nematic and isotropic phase Many tabetic· strategic* utiUe cmtsfcnking reaction* that ianoduce hainroyewniy into the ctenomr acnvoifc. over winch the I XT- changes shape TogeUkr. Acse factors often combine to creatr a applications where Acse soft actuator» interface with the human body and «aha sensitive

|MI l| Rloepriatiflg molaculat pattern» has often idled on liquid Cfynattmd (IJC> self imwbly of At monumcm which is frozenm by oodtnktaK to create the IXT. idle» via photopokmen/nct«m Ctilinnn command surfoeea. which have them «rives been paneraad mechanically. optically or topognptecally. an ana>· of LCP director panama can be generated' Lliliiaaoo of awautiupic magnetic Adds to dnve alignment ha» been rcaulied in 2 ^:< or 250· ^* gpiwnctries polyracrued in mold*. alAuugh Ac ability to build 3I> fiee-frams with arbitrarily vondatad IX ^* iwderieg remains doshc Harkening back in Finkehnan’s method for driving alignment via mechanicaJ «retching followed by crowlmkmfr. ecturion based methods have been pursued for additive fabrication of IJCF· * ^* . Shear imposed oa ohgumeric inks during ettwsion orients the nematic dweeh* along die print Arced on, which is opticady unwriiaked. determines the ifcrector field during fabneation of amcKwcupic geometries' ^* **. ¾ll of these are i< Mooted resolution and lack Ac ability to indeuMy define the molecular dweeior. voxel -bv-voxri

UUCP SI MMARY OF THE DISCLOSURE

|MI2| Many other variations are powNc wiA the preseat lidoturc and those and iriwr teachings. variatHwis, and advantages of the present dUdoanr wiH become apparent from the description and fijmra* of the dadowre

|SS13| One aspect of a pi drived embodiment of the prcacai disclosure oompnaes a four· macroscopic structures andtor anisotropic macroscopic materials having a plurality of vvxcK conqmsmg providing or forming a first layer of a photocuraMe first liquid cryoalVnc (LC> monomer, wharaia the first layer of the first I XT monomer has been provided or formed at a tamparamra foiling within a nematic phase mage of the first IX ^* mumwncr. applying a magnetic

- s- Md, taxing a fine thrce-dteentionil ("JO") magnetic field wetur with respect to an eripn pate of a JD oomdinmc system. to the first layer of ftist LC or one or more of the plurality of vends within the first layer of fun IJT monomer for a first dwell time, to produce in alignment with the (list ID magnetic field vector a fine molecular dnecan and/or first nematic aligament vector withm tire first layer of first LC monomer or within each of tire one or more of die plurality of voeels within the first layer of first IJT monomer, exposing the first layer of first LC monomer or dm one or more of the phnaliiy of voxels within dm first layer of first IX ^* to a first doer of light radiation, wherein the first dose of light radiation has a wavelength, iaiensity ati'er duration to pdvmcMC dm firm layer of firm IX ^* monomer or the one or mote of the plurality of voxels within the first layer of first 1 C monomer to a first polymerization depth; wherein the first molecular director and/or the first nematic alignment vector is preserved withm the polymerized portit* of the firm layer of firm LC monomer or within the polymerised portion of etch of the one n mure of the plurality of voxels within die firm layer of first IX ^* monomer providmg or forming a next layer of the first phoaocunblc LC and or a photocumMc second LC monomer wherein the next layer of die second IX ^* monomer tax been provided or formed at a temperaeue falling withm a nematic phase range of the second IX ^* monomer, applying a magnetic field, taxing a next JD magnetic field vector with respect to die origin pete of the JD coordinate system, in the next layer ofnocond IX ^* monomer or one or more of the plurality of voxels within the next layer of second LC monomer for a second dwdl time, to produce m alignment with die next 3D magnetic field vector a next molecular dnectnr and'or a next nematic alignment vector within the next laser of second IX ^* monomer or within each cf the one or mom of the plurality of voxels widen the next layer of second IX: monomer, exposing the next layer of second LC monomer or the one or mom of the plurality of voxel* within die next layer of second IX ^* monomer In a second dose of light radiation, wherein the second doec of light radUtion has a wavelength, intensity and/or dutaaon to polymerize the next layer of second IX ^* monomer or the one or mom of the pHimlitY of voxels within the acxi layer of second I C monomer to a second polymerization depth, wherein the next molecular director and/or the next nematic alignment vector H preserved within the polymerized portion of the next liver of second LC monomer or witiurt the polymerized portion of each or" the one or mom of the plurality of voxel* widwn the ecxl laya of seuwid IX ^* monomer

6 (OOI4J In another aspect of a preferred four-dimensional fMD ^" )-prmtmg or 4l)-additive manufacturing method of the present disclosure, the first molecular director is equal to or not equal to the next molecular director , or the first nematic alignment vector i> equal to or not equal to the next nematic alignment vector.

|0015| In yet another aspect of a preferred four-dimensional ( -lD'')-pnntiny or 4|)-«dditive manufacturing method of the present disclosure, the first I.C monomer and the second l.(! monomer have respective compositions that are the same or different

|0016| In a further aspect of a prefen ed four-dimensional ( 4D~j-printing or 4D-additivc manufacturing method of the present disclosutc. the fust dose is equal to or not equal to the second dose.

[0017| In another aspect a preferred four-dim cnsuxial C‘40 ^"' >-phndny, »* -ID additive manufacturing method of the present disdoAue further comprises: (g) in conjunction with the step la). forming a first part of a stimuli delivery svsiem inclusive of a first part i*T a conduit for delivery of heat. light or solvent stimuli to each of the first layer and next layers and-'or to each of the plurality of voxels. and (h) in conjunction with the step (d), forming a next pan of the stimuli delivery system inclusive of a next pan of the contlim for delivery of heat, light or solvent stimuli to each of the first layer and next layers and-'or to each of the plurality of voxels

|OOIS| In yet another aspect a preferred lout -dimensional (“4D ^** >-prinhm: or 4 D-iul thrive manufacturing mctlvod of the present disclosure further comprises repeating steps (dHh) as necessary until the anisotropic macroscopic structure or the anisotropic macroscopic material is complete

|0019| In yet anothci aspect of a prefen ed four-dimeriiavnal (~4D >printing or 4D-addilivc manufacturing method of the present disclosure the first and next molecular directors arc substantially the same as. parallel to. anti parallel to or different from one, more or all of the othci molecular directors, or the first and next nematic alignment vectors are substantially the same as. parallel to. anti parallel to or different from one. a plurality <x all of the other nematic alignment vectors

|0020| In anothci aspect ol ^' a preferred four-dimensuxial ("4D >printing or 4D-addilive manufacturing metlnxl of the present disci osme. the molecular director in each of the plurality of voxels of the macroscopic structure or macroscopic material is substantially the same as. parallel to, anti parallel to or different from one. a plurality or all of the other molecular directors of the others of the plurality of voxels.

[0021] In yet another aspect of a preferred four -dimensional ("4D")-printing or 4l>-addiiive manufacturing method of the present disclosure, the nematic alignment vector in each of the plurality of voxels of the macroscopic structure or macroscopic malenal is substantially the same as. parallel to. amiparalld to or different from one, a plurality or all of the other nematic alignment vectors of the others of the plurality of voxels.

|<M>22| In yet a further aspect of a preferred four-dimensional ( ^“ 41> >pcinting or 4I)-additivc manufacturing method of the present disclosure, each of the first I .C monomer and the second t.C monomer has a composition comprising one or more of a di acrylate tor providing temperature sensitive actuation, an d/nbcnzcnc-functionali/cd crossl inker for providing light responsive actuation, a photoinitiator, a IJY light absorber, and a visible light absorber and a polymerization inhibitor.

|0023| In >et another aspect of a preferred fixir-diinensitmal f 4D~hprintiny or 4D-addiiivc manufacturing method of the present disclosure, the x. y and 7 dimensions of each voxel arc approximately < 5U m 50 m 50 m or wherein the x. y and z dimensions of each voxel die approximately 20 m ' 20 m ^» 20 m

|0024| In another aspect of a preferred four -dimensi onal t ^** 4D">*pnnting or 4D-addirivc manufacturing method of the present disclosure, the first LC monomer and the second LV monomer have respective compositions tliat arc the same or different

|002$| Another aspect of a preferred embodiment of the prevent disclosure composes an anisotropic macroscopic structure or anisotropic macroscopic material produced via additive manufacturing, comprising one ot more layeis of a photocured liquid crystalline (l.C) monomer comprising a plurality of voxels; wherein each of die plurality of voxels of has a molecular director <* nematic alignment vector that is substantially the same as. parallel to. antiparallcl to or different from one. a plurality or all of the other molecular directors or nematic alignment vectors of the other of the pliuahty of voxels

- 8 - |MZI| In another aspect of a preferred anisotropic macroseopm structure or anisotropic macroscopic material of the present Asdoeure. a polymerization depth of the IX? mu m each of dm plurality of voxels is equal with or not equal with the polymerization depth in one. a ptumKtv or aM of the mben of the plurality of voids

|M27| In yet another aspocL a preferred saiiutropic atacrosoopic Urodmc or aaisotropie mcNDcgpk mamrial of the piocsii Asclosurc further cumprivrs ■ stimuli delivery *y<*em inclusive of a conduit for delivery of haai, light and** solvent oimufi to each of the phnahev of voxdk

|M2fi| to another aspect if a preferred aaisotropic macroscopic structure or anisotropic macroscopic material of the present disclosure, the sbnrali delivery system was produced by additive manufacturing al the une time as Ac aaisotropic nacioiefk structure or aaitoirofic macroscopic material to another aspect of i preferred niwinfic macroscopic structure or *ni»o*opk macroscopic material of the present Asclceure. the IJC monomer has a competition comprising one or more of a diaciyiaac for providing temperatore senskhre acmrion. aa aaobenaune· fimctionelired ciostiiakcr for providing tight responsive acmarioi, a photo* masks, a W light absorber, a visible light aheoriter and a polvaierualion iahihiiur

|MN| Another aspect of a preferred ewibodlrwent of the present Asdosure comprises artificial musde. soft robot, sensor or acrospncc system computing an anisotropic macroscopic stuciuic or anisotropic macrascoprc material produced via additive auoulacturing. comprising one or more layer» of a photocueed Squid crystalline monomer comprising a plurality of vends: n herein each of the plurality of voxd· of has a molacular Arector or nomaric alignment vector that is subsumiaMy the same as. paraUd to. anuparalld to or dinTcrcnt from ooe. a plurality or all of the other molecular Aredars «e nematic alignment vectors of tar other of the plurality of vtNveK

|ttJI| to another aspect of a preferred artificial musde soft robot, sensor or aerospace system of the presem Asdotme. the anisotropic macroscopic struct ute or aniwsrupic macroscopic material is capable of transducing one. a plurality or all of thermal, chemical, magnetic, aod light energy mto mechanical work

- 9 - |MS2| Another aspect of a preferred embodrinem of die present dfedosure comprises an maaufKturiag. comprising: one or more layers of a (fast photocurod liquid aym*int (IX") comprising a ⁽ inn plurality of wxds. one or marc layers of a second photocuied liquid aystoMuw ll£) monomer comprising a second plurality ofvoads; wherein each of dm fma and second plurality of vends of has a molecular director or nematic aKgamem vector that H mhsuetieMy dm same at, pardld to. anuparalld toerdiflereni from one. a plurality or Ml of ike ether molecular dueck*» or ncmabc alignment vucfcwx of die ethers of the first and second plurality of voxds

|NSJ| In another aspect of a preferred anisotropic macroscopic snuctui» or mwsotropre macroscupic material nf the present disdosunc, a polymerization deprii of the IX." moeomcr m each of vend of the first and second plurality of vends is equal whb or not equal with the polymerisation depth m one. a plurality or all of the others of the find and second plurality of voxds.

I**M| I* yet anolhsr aspect, a profaned anisotropic macroscopic souuuic ur anisotropic it disclosure further comprise* a stimuli delivery system inclusive of a conduit fin delivery of heat light andror solvent stimuli to each of the fuM and seoind plurality of vends

|M35| In another mpcct of a preferred anisotropic macroscopic structure or aouonppic maen copic muaid uf the |»oeei dukwwe, me stimuli delivery system was produced by additive mandheturing at the same time as die amsotropic macroscopic suvctiire or anisotropic

|tii)4| In yet another aspect of a preferred anisotropic macroscopic soucatre m anisotropic macroscopic material of the present dridmure. oacJi of the first IX ^* akmemei and the second I.C mooomar has a composition comprising one M more of a dtaciylatc for providing tcmpctaiuso sensitive actuation, an azobcnaene-funciionatied croud iakcr (far providing light responsive actuation, a photoinilimof, a UV light absorber. and a viable light absorber and a polymerization inhibitor.

|M37| ln another aspect of a prefeted sisoeopic macroscopic structure or anhniupic macroscopic material of dm prerent disclosure, the x. y and z dimensions ct each vend are

10- •s " JO m or wherein the y, y and / dimemions of aadi voxel monomer have respective corapoddooa dial are the or drUerera.

I··®*! Aaciher aspect at a preferred embodiment of the present dwdosunr comprises an artificial muscle. acA robot, sensor or aerospace s>«am comprising an anisotropic macmvuopic suuctwc or anisotropic macroscopic material produced via additive manufacturing. comprising one or more layers of a first pbotocurcd liquid crystalline monomer comprising a Urn plurality of voxels, one or more layers of a second photocurod liquid crysttllin# (I A ^* ) monomer composing a second plurality ofveadK wherein «ech of the fit* and second plurality of vuscls »«fhas a moiecutar dtaecaoror msnabc alignment vector that is sabeamuially the same as. parallel to. aatipasahol to m difleran from one. a plurality or a* of the other molecular directors or nematic alignment vectors of the others of rite first and acooad pi uralitv of venal*

| ^§ 94·| In another aspect of a preferred artificial musdc. ML robot <ens*r «w aerospace xyrtem of the prcaaat disclosure, the aaisowopk macroscopic structure or aniaotropic macroscopic atatcrial is capable of transducing one. a plurality or all of formal, chemical, magnetic aad light energy into mechanical work

|W4I| Aaothcr aspect of a prefened cmbodmteai of die praaani disclosure com pines a compomtioa comprising SS -W WL% manynic : 05 - 2wtS phoroiak . and 1 - S wiSUV ahambet

|W42| k vet anodici aspect a preferred comporitioa of the present deckwurc farther comprises 0 l · 2 wt % polymerization mhibitor

|tdU| Another aspect of a prcfciiod embodiment of the praaani disclosure compose» a composition compriwag *5 - 95 wt% mesogcok monomer. I · 12 of a iuactionali _/ cd oossS nicer tor «adorning light responsive acaattoa. andO < - 2 wt¾ phoioimtiaaor

|M44| In yet anothci aspect, a pmfarrcd composition of die present disekmac further comprises 0 I -05 wi %«fa visible light absorber. II [0045| In another aspect of a preferred competition of the present disclosure, the mesogenic monomer comprises 2Alc<hyl- 1 ,4-phenylenobis[4[3(»cryloykixy ) propvloxyjtvcnzootc] <RM2<7)

|0046| In another aspect of a preferred composition of the present disclosure, the photoinitiator corn prises 2-Bc*iz>l-2-dimethyUirmno- 1 -<4 morphoimophcnvlK-buiammc- 1 (Irpacurc 360)

|0047| In yet another aspect of a preferred composition of the present disclosure, the pHotoinitiaioi comprises Irgacurc 784 (C'tba specialty chemicals)

|0048| In another aspect of a preferred composition of the present disclosure, the I L ^' -absorber comprises 2-<2H-Benz«itriazol -2-yl)-4/>-tli-tcrt pcm>lpheno1 (Tinuvin 328)

|0049| In another aspect of a preferred composition of the present disclosure _, the photciniti.it w comprises 2-Benzyl-2-dimclhyiamino-l-(4 morpholmophcnyl)-buian<fu>I (Trwacure 369). and wherein the UV-absorbei comprises 2-<2I MWn/otriazcil-2-yl)-4.h-di-tcn-pentylphenol (linuvtn 328)

10050) In another aspect of a preferred composition of the present disclosure, the polymerization inhibitor comprises rnethylhydroqmnone

|0U51| In yet another aspect of a preferred composition of the present disclosure, the photoimtiaior comprises 2-6en/yl-2-<limcihyI amino- 1 -(4-morpholmophenyl )-butan«ie- 1 (irgacurc 369 ⁾ wherein die l.- ^' V-absoibcr comprises 2-(2H-Bcnzotriazol-2-yl)-4.6-<lHcTV pvnr> Iphenot (Tinuvin >28). and therein the poly mci i /at· on i riliitx tor* comprises methyl hydroquinonc

(0052J In another aspect of a preferred composition of the present disclosure, the functionalized crosslink*» for endowing tight responsive actuation comprises 4,4-di(6-0rcryloxy)- hexyloxy )azobervcm: (Azo 6c).

|0O53| In another aspect of a preferred composition of the present disclosure, the visible liyht absorber comprises Methyl red ( 2-< 4-Oi methy I ami nopheny lazo ^' ibenzoic add. 4

DimeUi>laminoazobctvciH>2'-carboxyTie acid. Acid Rod 2 jaiichascd from Sigma- Aldrich).

[00541 Another aspect of a preferred embodiment of the present disclosure comprises a composition composing 98 wt.% mesogcriic monomer. 1 w t % photoinitiator, and I l.V- absorher

G Effff A torthcr aspect of a preferred embodiment of the present dudonve comprises a

IV^bMibcr

|MS*| Another aspect of a preferred embodiment of he pmwm dhekwuro comprises a composition comprising 95 wt S mnsogenlc monomer. I wt.S phoaoimtmMn. and 4 mt.% IV-

|M57| Yd Mother aspect of a preferred embodiment of the praaam disclosure comprises a composition comprising 973 wt% menogamc r, I wi% pholoiakiaauf. I wtS I V. absorber; and 0 $ wt % pdvmenzaiion inhibitor

|N5I| Another aspect of n profaned embodhaem of the present discfcmne oomprbes a eumpociiion comprising: mcaogouc asonormy. 10 MS of a functionalized crossfiaker foreodowmg light responsive actuation and I wtS photoinidator.

|9t99| Another aspect of a profaned embodiment of the present disckeure comprises a compoeioo comprising.· 88.0 wi% mcsogcnic monomer. 10 wi % of a functional iacd croediaher fui endowing hyN responsive actuation. I photemitiator. and 0 I wt % of a visible light absorhei

|8Mi| Another aspect of a preferred embodiment of the present dudotui cumpriscs a system lot tourdimensidnal i ^e 41> >pnoiiiig or 4lX^ddm\* mamAcmneg of anisotropic maercuoopic tfiuctarm wd'or anisotropic macroscopic materials eompnsm* one or more ptoeuruml 6<pwl oynalKnc (L<:> monomers having a plurality of voxels, wheroie each nf the plurality i€ voxels of has a molecular director or nematic alignment vector that it substantially the same as. parallel in. anti parallel to or «Efferent Horn one; a plurality or all of the other molecular directors or nematic alignment vectors of the other of the plurality of vends, comprising a build plate, a motorized translation stage tor moving and controlling the position of the build plate, one or more magnets mounted on a motorized rotation stage for rotating the one or more magnets shout or around the build pbt* to impose and control a direction of a magnetic field thorn or around *· build plate: a l)Mf> irradiation p«jedor having a kn>, wheroie the lens h mounted m hnc with the build plate, a heating system tor controlling the LT monomer temperature during printing, wherein die heating sysum comprises n ring disc heeler, temperature controller, one iv moro thermocouples and a thermometer, and whgrdn the ring dfec heater has an opening through

13 which the lens of the DMD projector extends, a bottom window disposed above the lens of the DMD projector, a rig assembly or frame for integrating the build plate and its motorized translation stage, the one or more magnets mounted on the motorized rotation stage, the DMl) projector and lens, the heating system and bottom window.

[0061] In another aspect of a preferred system for four -dimensional t"4D ^"" >-pfinting or ID· additive manufacturing of anisotropic macroscopic structures and ^' or anisotropic macroscopic materials of the present disclosure, the bottom window comprises a clear acrylic sheet

[0062] In another aspect of a preferred system for lour -dimensional (“4D ^’ ’)-priniing or 4D- additivc manufacturing of anisotropic macroscopic structures and'or anisotropic macroscopic matenals of the present disclosure, the bottom window is coated with PDMS (Sylgard 184 Dow Coming 184 Silicone Klaxtomcr)

1006)] In another aspect of a preferred system for four dimensional ("4D")-priniing or ID additive manufacturing of anisotropic macroscopic .structures and or anisotropic macroscopic materials of the present disclirsute. the motorized translation stage controls the movement and position of the build plate in one or more axes

[0064] In another aspect of a preferred system for tour-dimension ai ("4D'i-printiny, or 4D- additive manufacturing of anisotropic macroscopic structures and'or anisotropic macroscopic materials of the present disclosure, the motorized rotation stage is capable of controlling rotation of the one on more majrncts about one or more axes

[0065] In another aspect of a preferred system for li ir -dimensional ("-tD ^"" ) printinc; or 41)- additive manufacturing erf anisotropic macroscopic structures and/or anisotropic macroscopic material* of the present disclosure, the DMD projector has no LY fillers.

100661 In anotlici aspect of a preferred system for foui -dimensional ( ^* -tD' ^* )-printini2 or 4D- additive manufacturing of anisotropic macroscopic structures and'or anisotropic macroscopic materials of the present disclosure, the build plate has been spin-coated with hl\ amide (DuPont j to achieve adhesion between the cured material and the build plat*

100671 In another aspect of a preferred system for four-dimensional (“4D ^" )-pnnl ng 01 4D- additivc manufacturing of anisotropic macroscopic structures andor anisotropic macroscopic

11 materials of the present disclosure, the build pi ate has been rubbed in one or more directions to impose an alignment on mesogens within the LC monomer close to the build plate

10068] Another aspect of a preferred embodiment of the present disclosure comprises an artificial muscle or soft robot comprising an anisotropic macroscopic structure and-'oc anisotropic macroscopic material comprising one or more layers of a phutocurcd liquid crystalline (l C) monomer comprising a plurality of % axels, wherein cadi of the plurality of voxels of has a molecular director or nanatic alignment vector that is substantially the same as. parallel to. anti parallel to or dilTcicni from one, a plurality or all of the other molecular directors or nematic alignment sectors of the other of the plurality of voxels, whcicm the muscle or soft robot is capable compound movement such as the ability to change shape and-’or length other .simultaneously or non-simultaneously and-or such as the ability to extend and twist simultaneously and-’or to contract and twist simultaneously

BRIEF DESCRIPTION OF THE DRAWINGS 100691 The present disclosuiv is illustrated by wav of example and not limitation in the figures of the accompanying drawings, in which:

|0070| FIG. IL shows a schematic of a layer-by-layer 31) printing system of the present disclosure capable of fabricating three dimensional geometries with mol cedar alignment encoded using a magnetic field-

100711 FIG. IB shows an example of control over the molecular director within a given layer using the system of FIG. 1 L

J0072| FIG. 1C show* polarized optical microscopy (POM) images of a sample with mutually orthogonal molecular orientation, which wax generated using the system of FIG. I A

|0073| FIG. ID shows the ability of a preferred system of the present disclosure to pattern arbitrary features, while achieving molecular alignment by printing a bi layered.

|0074| FIGS. IA-2B show polymerization depth as function of irradiation energy dosage for various compositions of the present disclosure

|007$j FIG. 2C illustrates a scalable fabrication of molecular! y-oulcrcd solids created with individual lOOum layers according to the present disclosure

- i s - |W74| FIG. JA shows hamcming the respume of a 3D printed bflnyerad actuator in overourvanwe-driven assembly of Gaussian ouved geometries in a preferred cumposrrioo of the

|W77| FIG. 3B shows light responsive array of microerucmrw ftbrkned in accordance with the proem dtdotun: usiag a preferred compocttioo of the present disdoaure

|W7S| PIG. 4A shows a Aanefttsi for modularity composition of a svuctur· between layan fabricated in urordaace with the present dktow?

|M7f| FIG. 4· shows a 2-axis robotic ami. which is diicctly ID priated to icnKzc responses to Mewl stimuli in the diflacnt joints in amadancc with *epob«ntdhdo«une.

R··H PKSSw 5 and 4 show optical waveguides, each made in accmdancc with the present disclosure.

|09bI| PIG. V shows a preferred JD primer setup of the pres tat disdoaure and its components comprising a magnet build plat*, a PDM$ substrate, a hot stage and a DI.P projector

|W2| FIG. · shows black and whist 2D patterns used ftr ftbncanag the bdaver basket of FIG. 3A according u> the present disdoaure

|M3| FIGS.1A and PB JJKJW ovcreurvalure driven transformation of structures of the basket- like geometries due to thermal actuation according to the present disclosure

|Wt4| FIG. ISA shi*v> a dueo^itncmioaal CAD modd of the light responsive array of nucroetnwiwc» of FIG.3· rubricated in accordance with die present iksdosure using a preferred composition of the present dtolntutr

|MtS| FIG. I SB show» pawn used fur making the right responsive array of rmcroenuauics of FHi.JB fabricated ia accordance vriih rite prewmi dhdoaure uang a preferred composition of the present disdoaure

DCTAILKD DESCRIPTION

The following description, taken in cnojeaction with Aa referenced drawings, is presented to «ruble one of ordinary skill ia the m to make and use the disdosurc and to incorporate n m the context of partiarlar application» Various modifications, as wdl as a variety of uses in different appKcadeox will hr leadfly apparent to thouc skilled in the art. and the

• Id · general principles, defined herein, may be applied to a wide range of aspects The present disclosure is not intended to be limited to the aspects disclosed herein Instead, it i> to be afforded the widest scope consistent with the disclosed aspects

|00$7| The present disclosure presen i> a framework for breaking out of the coniines of pnoi approaches by exploiting the combination of anisotropic magnetic susceptibility of the LC monomers and spatial ly -selective photopolymcrizalion using a digital micromirror device (DMD) in a bixtom up (inverted) 3D-ptinting configuration The system * illustrated in FIG. I A and FIG. 7 utilizes an indexable 300ml magnetic field (II) generated using permanent magncis 10. 12. which are mounted on a rotation stage to drive alignment of the IX monomers A DMD system 14 (Viviick DV121ID projector) with a pixel resolution of -50mih polymerizes desired region* to preserve this orientation with spatial selectivity Independently dictating the alignment using a reoncntable magnetic field and polymerizing as needed to build a ID free form liycr-by- layer allows for fabricating structures, where the molecular alignment and the geometry can be defined in a truly voxd-by voxel fashion furthermore, during the fabrication of each layer 16 _, the monomer i< confined m a build-gap I* between the prior polymerized layer (or the hmld plate IV. if it is the first layer) and a PDMS (Poly dimethyl si loxanc) substrate 20. After selective polymerization under the influence of a leorientablc magnetic field, the polymerized laver i* detached from the PDMS substrate 20 bv retracting the build-plate IV to create the subsequent build-gap 18. The sample 15 remains attached to the build-plate IV during the build process and after each retraction of the build-plate IV a fresh monomer mixture (of same or different composition) t$ introduced. The process is then repeated This framework also allows fm arbitrary modulation of the composition of the materia! from one layer to another functional gradations become possible to integrate multi-roponsivencss in a facile manner to create response profiles, which were hitherto inaccessible rXTRODl.CTION

|0088| Regulating functional properties and directing structural evolution in active polymers by programming composition and microstiudural gradients during fabrication it a versatile route for realizing soft machines Integrating active dements with suspensory structure _* . including fluidic ¹ and solid ‘ mechanical logic dements has been used to encode macroscopic actuation and manipulation in soft robots If individual voxels of a material themselves become capable of

- p active functionalities, a broader design-space of encodahlc responses can emerge by blurring distinction between the active and the suspensory, structural elements The material itself, becomes the robotic manipulator. Tor example, programming anisotropic magnetic domain structures in magnetic particle-infused polymeric inks can enable soft lubots. which manifest non-linear shape transformations using magnetic ftdds ’ Biomimtrtic transformations haw also been realized via anisotropic swelling m structures ID printed with aligned nano-cellulose fibers* Hie underlying organizing principle is to exercise voxd-by-vo.xd control over both the geometry and the anisotropic coupling between a stimulus and material response When responsivenes-s geometry and mechanics conspire, emergent design opportunities become possible

|W39| Liquid ciystallinc polymers (LCP) are distinguished among stimuli responsive materials due to their ability to reversibly generate work densities in excess of J 'ke with unusual force- displacement characteristics. Notably, the ability to simultaneously generate large strains (IOV'«) and actuation stresses (100 ^‘ s kPa) from order-disorder transitions of the long-range orientational order in the macromolccular network ^' Actuation can be induced using a range of stimuli, including heat light and solvent ^M Typically, principal directions of actuation strains are derived from the anisotropy of the molecular director contractile strains arc generated parallel to the director and tensile SUM ns emerge perpendicular to it ^l0 . Blueprinting spatially heterogeneous molecular patters to direct the large work potential is a compelling feature of the

IL'R '* This allows for their utilization in actuators across length-scales ranging from the micrometer- to the macroscopic- scale : i . i . Turthermore. exploiting the competition between bcndiniy ^’ strctching in slender ob _j ects allows for eliciting the rare combination of high- foreevlarge-displaccmcnt actuation from hitherto small form-facini actuators ¹¹

|U090| Blueprinting molecular patterns has often relied on liquid cry aniline (I.C) sdf-asscmbly of the monomers, which is frozen-in by crosslinking to create the Lt.’P, often via photopoly mcii/ahon Utilizing command surfaces, which have themselves been patterned mechanical lv. optically or topographically, an array of t -CP director patterns ean be generated ^u Utilization of anisotropic magnetic fields to drive alignment has be resulted in 2 ¹⁴ or 2.SL) ¹⁵ geometries polymerized m molds although the ability to build 3D free- forms with arbitrarily voxdatcd 1.G ordering remains elusive Harkening back to I ^' inkdman ^' s method for driving alignment via mechanical si retching followed by crosslinking °. extrusion-based methods have

- 18 - been purtiwd for additive fabrication of IJCP Star imposed on oligomeric inks during etiueion orients the nematic firoctar along the print direction, which to optically crosstinked. soon after the deposition. The pattern, which is defined during the build sequence detenmaw die director field during fabrication of macroscopic geometries ' ^* *

|dt*l| KxpMdng the full porndd of LCP in ad^Hve strocaacs end mechurisms requires an ability K> ddtoe the molecular onemauon. vv%d -by- voxel during the fabrication of a 10 Ace- form Uoing *i. holds dm key in cncodmg arbitrary namfumt ioee of 3 di dons picdcfined target metrics ^w , which is defined for each voxel This unlocks a pndiway for datiyeog transformable 30 promotes. iaduding complex active kinematic and machamcal logic units, brommickia* actuators ami hamming magmfkd actuation profiles in <oO robotics ('urreni ftbrieation approaches constrain the ability to access this 31) design The command surfocetaed methods era mninucalK hunted to flat goumctrics (typically film» <100 umk ncccnwtating lamination-based atnamWy for scaling the raspiwishencss *. Fabrication tn mold» Rmits geometnos to those, which can he tchabhr extracted following pohmetuabon 1*1% Ocpcetiontaod methods can generate arbitrary geometric», but they armor decouple ■deed* pattering from the build sequonce l*M approach, where the mofocufor arieatatioa be mdcpcadeady defined with say. G loohitiun per <0pm element Fur a I mm segment. the latter method ofleix a design-space, which i» larger by a factor of -hi" in compartoonio the deposition-based method Assuming. ISO ^* is available nidi I* mol urine prt V>)in kngih riw inral nusnber of design permutation» ii nw‘ ^,w,x> 10**' For a I nun ¹ volume, the design space is large by a goopol.

|tt*2| Ikre. we present a framework for breaking out of die confines of prior »rr ^fin * ^<,hit by exploiting the combi nation of anisotropic magnetic susceptibility of the LC i» and spatiaiy-sdeedve photiyoKiwcriaaon using a digital micromiiror device (DMD> in a bottiwn- up (inverted) 30-priuting configutatiun The system iltatratcd in FIG. IL ( also FIG. 7.

Supporting Information) utilizes an indexable 300mT mtpnitir field (II) genemod using permanent magnets It. 12. which are mounted oo a rotation stage to drive alignment of the if monomers. A DMD system 14 (Viviiek 1)012110 projector) with a pixel resolution of 50pm polymerizes desired regions to preserve this orientation with spatial selectivity Independently dictating the alignment using a roonontaHc magnetic field and polymerizing as needed k> build a

10 313 free form layer-by-layer allows for fabricating structures 15, where the molecular alignment and the geometry can be defined in a truly voxel -by-voxel fashion furthermore during live fabrication of each layer 16, the monomer is confined in a build-gap IS between the prior polymerized layer 16 (or the build plate 19. if it is the first layer) and a Polydimcthylsiloxaric (PDMS) substrate 20 After selective polymerization under the influence of a rex >ricn table magnetic field, the polymerized layer is detached from the PDMS substrate 20 by retracting the build-plate 19 to create the subsequent build-yap 18 The sample 15 remains attached to the build-plate 19 during the build process and after each retraction of the build-pl ale 19 a fresh monomer mixture (of same or different composition) is introduced The process is then repeated This framework also allows for arbitrary modulation of the composition of live material from one layer to another Functional gradations become possible to integrate multi-responsiveness in a facile manner to create response profiles, which were hitherto inaccessible

|0093| Building LC ^’ P in this fashion encounters a constraint where a given voxel or a layct influences the patterning in a neighboring dement which is subsequently built. Consider the example of a multi-layered geometry m FIG. 1A. where layer n has an orientation which is transverse to that in the monomer in the build-gap below it The monomer will eventually become layer n / with an orientation determined by the magnetic fidd The spatial extent to which the alignment in the layer n · l. will be influenced by the anchoring from layer tt will determine the finest resolution capable with this platform This is essentially parameterized by

TV f«ermeV«i magnetic coherence length (4). which lor a JOOmT magnetic Held is z -

H \ F r _n

10 mt ^h assuming LT ₂₂ ~10 ^-, ά)ΐk: (twist Frank constant) and jr _o -10 ^-/ (thc anisotropy of magnetic susceptibility in c K-S ) Ji-.V In a typical voxel Hi urn < SO mm ' 50 pm. when the characteristic dimensions arc much larger than x. the effect of anchoring from adjaccni voxds declines exponentially and the alignment will he essentially dictated by the magnetic fidd ⁷¹ lienee, for the resolutions targeted lierc. this platform becomes viable for lavcr-by-laver fabrication of molecul arly-ordered tree-forms, where within each layer 16, the <ii rector can be controlled voxel-by-voxel

(00941 FIG. 1A shows a schematic of a layer -by-layer 3D printing system 8 capable of fabricating (hire dimensional geometries 15 with molecular alignment encoded using a magnetic field Reorienting tire magnetic fidd on demand and spatially selective polymerization using a

20 - DMD light source 14 allow for independently indexing the molecular orientation voxel -by -voxel See also FIG. 7 for an illustration of the physical setup of system 8 of the present disclosure Fit·. IB shows an example of control over the molecular director within a given layer 16 A build-plate with an alignment layer is used to trigger a preferred alignment three ti on Application of a magnetic field reorients this alignment, which is selectively frozen -in via crosslinking. Then, the magnetic field is rotated to coincide with the prior orientation, following which crosslinking is used lo ptvsctw the patterning FIG. 1C shows polarized optical microscopy (POM) images 22 of the sample with mutually orthogonal molecular orientation, which was generated using the steps described with respect to FKL IB above The regions with uniaxial alignment are bright (maximum light transmission through the material) at 0 degree and dark (less light transmission) at -15 degree under parallel polarizers (images m the left) ami dark at 0 degree and bright at 45 degree under crossed polarizers (images m the right) Other regions arc characterized by a patter, which is rotated through die thickness FIG. ID shows ihc ability of system 8 of the pi event disclosure to patter arbitrary feature*, while achieving molecular alignment by printing a bi layered gear-shaped structure 25 ^‘ Ptc exploded view of the structure and the director orientation for each layer is shewn The build plate, similar to FIG. IB and FIG. 1C", is composed of a rubbed dvamide layer, which enforces a preferred orientation The first layer 26 is created by applying a magnetic field orthogonal to this orientation, which leads to a rotation of the director. Second laver 27. which consists of the hub and teeth of the gear is rotated with respect to the fust layer to reset the alignment with respect to the robbing direction on the build- plate Ihc images on the right are POM images of the first layer and the final bilayer structure at 0 degree and 45 degree under parallel and crossed polarizer (P) and analyzer (A) (All scale bars 1 mm).

|0095) This platform docs not restrict the molecular director to a fixed orientation in a given layer FIG. IB. illustrates the creation ot ^' multiple nematic orientations m different voxels of a single layer lo demonstrate the idea, a glass huild-platv was spin-coal eil with Flvumidc (DuPont) and rubbed to create a surface anchoring condition (along n _A ) to emulate a prior layer and n is positioned 5(¼im away from a POMS substrate. L monomer mixture (RJPIT4 m Table I ) composed of ri* wi % moogcnic monomer RM2>7 (2 Mclhvl-l _» 4-phenvlene- bis[4[3(acryloylo\y) propy lo.xvjbenyoatej ), 1 wi · _* phoiomitiatoc Irgacure >60 (2-Bcnrvl-2- dimcthvlammo-l -(4-morpholinophcnvl)-buLanooc-l ) and 4 wt % 1. V-ahsorbcr Tinuvin 328 (2-

? 1 (2H Henzotriazol-2-yl)-4,0-di-ieil-pent>lphciUl) wait introduced in Uic build-cap A constant temperature of 1 W( ^" was maintained and a JUOmT magnetic fidd was applied perpendicular (in plane) u> the surface anchoring direction for 300s (dwell time). Selective photopoly mm zari on (with O.tt s exposure and 170 mW cm ^' ) using the DMD system was used to crosslink regions with a director pattern, which is rotated by x/2 with respect to the prior alignment Alter which, the magnetic field was rotated to restore the axis with iw in the unpolymcrized regions. Meanwhile alignment of the already cmssl inked regions remains fixed. Crosslinking of the remaining monomer was then used to generate a striped sample with alternating layers of uniform alignment alone n _x m some regions and rotated nematic patterns in the rest FIG. 1(.' ill usar ales the pdaii/od optical microscopy ( POM) images of a single layer built using this idea The parallel and crossed polarized images illustrate regions where the director patterns are all aligned along n _v ot are rotated perpendicular with respect to » by the magnetic field

|0096| At this point, it becomes possible to marry spatially -selective polymerization with spatially-resolved blueprinting of the director patterns to build geometries layei -by -layer FIG. ID illustrates a tw<>-l«ycrcd gear-shaped structure 25 Mere, l he first layer 26 is characterized by planar orientation of the nematic director (perpendicular to the nibbing direction) _, where the corresponding geometric profile is sdectivdv built Then, the built-plate is raised, monomer is introduced into the build-gap and the magnetic fidd is oriented transverse to this orientation 1 hen, the teeth and the hub are selectively polymerized with the rxxatcd orientation. Ihe POM imago were receded nfier the first layer 26 was built and alter both lasers 26. 27 wne created FIG. I D illustrates images with both crossed polarizers (polarizer P perpendicular tv analyzer A ) and with P parallel to A for each case.

TaNe 1. 1 Teat and light responsive monomer mixtures of various compositions. their curing temperature and parameter* character! /in i; their working curves in HCS. 2A-2B.

|0097| Parenthetically, we note the presence of a temperature window for orienting and polymerizing the mesogeme monomers without requiring anv temperature cycling The ability to 3D print molecular ly-vrdcrcd polymers at a constant temperature eliminates in process deformation of the responsive material and added process time due to the hearing-coding evdea Often, tcmpeiaturc cycling into the isotropic state of the monomer followed bv cooling into the nematic state in the presence of an orienting fidd has been used ¹¹ Eliminating this thermal cycling decrease» the possibility nf thermal curing of the monomer during the printing.

RESUl.IN AND DISCI. SSION

|0098J When seeking to create complex geometries with highly defined structural features, the ability in control the polymerization depth in individual polvmeii/cxl voxels becomes critical We find that the interplay of the optical absorption of absorbing dyes and relative concentrations of photoinitiator and inhibitor of polymeriaauon provides control over the depth to which crosslinking occur* within the build-gap But for this control, as the material is built unintended polymerization can occur, especially when overhanging structures ate fabricated in subsequent

- 23 - 1 ay era To achieve this control, while simultaneous! ₎ achieving molecul arty -ordered I .CP. a range of monmnei mixture* were developed RM257. a di acrylate, was used as the host mesopen. which generate temperature sensitive actuation Doping with zm azobcnzcnc- functionalizcd ciossl inker l Azoix) endows light responsive actuation Details can be found in the experimental section. For the compositions shown in Table 1, the polymerization depth (/.>,) is found to be a function of the photonic energy dosage ( / /). where / is the intensity and / is the exposure time Wc utilize the scaling relation: D _p — D„\T\ ^ Vy^)· 'frhere / ^>,Ί *«d (J. arc constants characteristic of the monomer mixture V FIG. 2 A illustrates the "working curves for the various compositions in 1 able t . />, encapsulates the eiYect of attenuaiion of light through the monomer and its clTcct on the depth to which polymerization occurs. .An effective approach for controlling this parameter is via the addition of the absorbing dyes For therm ally-responsive RM257-bascd resins (FIG. 2L). controlling the concentration of the l.V absorber (Irnuvm) leads to a smaller />, Sec FIG. 2A for comparison of RIPlTl v$ R3P1T4. where the slope of tlx- working curve i> smaller with increasing V V absorber Ihc effect of the photoinitiator on the slope however is small ax «eeti from the cumpanxon of R3PIT1 vt R.1P0 5T1 These systems are polymerized using Irgacure ihO (Ciba) as photoinitiator and using unfiltcrcd irradiation from the projector, which has components from UX to visible In contrast, the azobenzcitc-functionali/cd materials aie polymerized using light filtered with a 40<nm long-pass filter to avoid iscmcrizing the azobenzene during the polymerization Here. Irgacure 784 (( jha) is used as the photoinitiator and Methvl Red is used as the absorber The working curves for the phoforesponsive resins ane illustrated in FIG. 2B We identify compositions and processing conditions to ovcicxxnc challenges in the incorporation of phocochromic molecules, which modify the stability of the meso phase and present challenges m crosslinking mo*x*mcts with spatial selectivity to preserve the molecular order ²⁵ Ihc constant (A- in FIGS. 2A·2B is correlated with minimum energy density that is requited to start the polymerization which increases when the amount of photoinitiator is decreased. Ihis can be seen by comparing {> for R3IM 11 vs R3P0.M 1. Similar increase in the O.· is observed when a polymerization inhibitor (methyl hydroquinunc) i$ added in the composition R.31’1 11 IV * Increasing Q _t leads to a shifting of the working curves to the right, wheiein the intercept along the x-axis (energy dose) increase* These calibration curves enable the scalable fabrication of raolccularlv-ordcrcd freeforms at scales, which outstrip conventional ce114.vtM.xl fabrication methods. while also enabling precise control over the geometry FIG. 2C

- 24 - iHmtmts a pyiamiddiltc emetine Jt fabricated witii RJPI GI. who· the molecular director (n) drought* the sample is oriented dong dm mdkated anew SI. The pyramid 38 is 3 * mm high made of 31 layers wi A IUO am layer thickness. A _< to molecular patterned sunourcs at the* scale» hold* the hey to magrafyint; the mrfc potential and the utility of IJCP acuiason ia

I··*·! FIGS. U4B Aon pohrmen/asion depth m functuwi of imdration energy dosage for varitws eompoeitioe» w laMc I. he# responsive U P mixmrui in PIG. 2A and azobcnacae· fancoonalieod light responsive mixhse* H» MG.2B. FK2.2C iNustrmes a scalable fabrication 3· uf mdecdatly-ordwud solids eeaied wuh individual lOOpm layers T¼e diiectioa of the ncnucic Ancux in the Miuauit fabricated with fabricated nidi R3PITI is illustrated via tbc blue arrow SI («ale bar l mm)

I····! The ability to fabricate mnlcuriariy-ordctcd Onesforms allows far hanurong noa-Kncar mechanics to enable new petiiways Aw shape sakection. Coasdcr. a bdaycrod struct unc flat strip priated using IIPI 11 m FIG. SA. where a uniformly oriented monudomain sample of 30 «on in tbicinuKs resides on randomly uricaied substrate of 90 «an dhckncss. The nuwiodomain sample is created by polymerizing the «nip M under a satfanarv magnetic field while the random pdytkwnaia piwtfan is ermted bv polymerizing in tbc absence of a magnetic field The mddi of die sample ia the tiuid dimenaon is 09mm The monudomain portion will respond by shrinking along die long-axis, while «be polydom»· sample produces mi net strain As a result, heating the sample lead* m a curvature of the Mayer S7 (a 0.98 mm ^* '), as ill ue fated Hie ability to directly fabricate complex geometric» to exploit mechanical eoadiaearitics tital dkit unusual shape transformation». a btlaycr basket shaped configuration 38 urns priated llcm. a nag-shaped miucturc was printed, segmeot-by-tegmem (sue FIG. ·). with the diiector pattern, which is azimuthally oriented lhis ring can also he thought of as an annular section of a · I topological defact “ The was integrated with a subsequent layer, which was printed with a squaic weave hatched pattern and a polydontaia alignment, ia thcabscaceofa magnetic fidd

|·1·I| This composite structure allows for exploiting the idea of overcurvatara to create geometries with a Gaussian curvature, even when malting from a prior fiat state v While a bi layered fiat strip will bend whoa heated, confining die bilayer into a dosed ring with a cmvanro onhogooal m that generated with hear can trigger budding on of rite plane. While this

- 2« ha* been explored in die buckling of rods ^* \ here. we exploit O»M fabrication platform to drive transformations of surfaces from a flat state into one characterized by a negative (lOussian curvature l he overcuivatine is defined by the parameter 0 _p = _v ' 1 t (nr/?) ² . Where k is the curvature caused by the heat actuation (same as the curvature of the flat hi layered strip after heating) and is orthogonal to the in-planc curvature R ‘ ¹ . At room temperature O, 1 <tc Uk the geometr ^y is flat with an initial curvature R ^' H 26 mm in FIG. 3A By increasing the temperature (> > ft), the ring generates an orthogonal curv ature k As the periphery of the sample buckles out of plane to minimize the bending and torsional energies, the hatched surface 39 is forced by the constraints along its periphery into a negative Gaussian curved shape By modifying the value of R. differing levels of over curvature can be accessed to create a range of geometries following thermal stimulation (see FIGS. 9A-9B Supporting Information)

|0I02| Vlonomci system R77PI R0 I was used to demonstrate the fabrication of light responsive mictostructuros in FIG. 3B A/ohen/ene-functionali/exl mixtures result in a glassy T CP. which respond to irradiation with 505nm L'Y by bending towards the actinic light ³¹ Ilie ability to spatiotctnporally modulate the actinic light to direct actuation in microstmcturc» is particularly attractive for dealing functional surfaces and active topographies In contrast to prim approaches, involving cholesteric self-assembly * or mi cr moulding ^u . the design space possible with die 31> printing approach is broader, including opportunities creating reentrant mi ci structures, which are capable of unusual properties (e g robust superomm phobic responses ^• ^) FIG. 3B illustrates an 8- 6 array of met hanging cantilevers 40 mounted on pillars 41 with different heights (also see supplementary FIG. I0A) The idea is to demonstrate fine structures composed of reentrant features, which arc responsive to light This system was polymen zed using light filtered with a 495nm long-pass filter to avoid isomcii/ing the azoben/vne during the polymerization The pillars 41 have polydomain molecular orientation and the molecular directors in the monodomain cantilevers are aligned parallel to their long axis as illustrated in FIG. 3B Cantilevers 40 arc GO urn thick and 700 gm long During the sample development to wash off residual mommas after finishing the printing process, the capillary forces from the solvent bent the cantilevers 40 downward. This, can be solved by utilizing support structures which are removed after the development When, this structure is irradiated frym the Kip. the absorption of light by the overhanging cantilevers 40 leads to their bending towards the light The deflection is illustrated by tracking the outline 42 of the cantilever 40 as illustrated in FIG.

?6 3B (also, see SI Movie 1 ) Graded contractile strains (- -1 K% strain on the exposed side) arc generated along the nematic director. which generates the bending Strains were calculated by measuring the change in the curvature of the cantilevers (Lk) and the initial bending angel (a). After the UV light was turned oft ^* , the cantilever spontaneously relaxed to its initial shape after - 30 minutes at ambient temperature The ability to fabricate such responsive microsmiciurcs along arbitrary an face profiles can hold the key to modulating functional responses. including hydrophobicity, fluid drag and biological responses

FIG. 3A shows harnessing the response of a 3D feinted hi layered actuator in ovetcurvature-driven assembly of Gaussian curved geometries in R3PITI. A strip 3$ composed of a uniformly oriented I -CP residing on a polydocuun l.CP (punted without applying a magnetic field) generates a curvature «I. when stimulated with heat However, creating an annular geometry with an azimuthally-pattcrned director, which resides on a hatch -patterned suspensory structure 39 (polydomain) elicits the creation of a Gauvsian curved saddle-like geometry 37 _, when healed < scale bars - I mm). Ihe exploded view of the hitherto flat geometry before healing is also illustrated FIG.3B shows light responsive array 45 of microsimcturcs fabricated with R77P1R0 I. Ihe overhanging cantilevers 40 are monodomain, while the vertical pillars 41 are poly domain liradiation w ith 305 nm UV elicits a bending of the cantilevers 40 Red dashed cvtiincs 42 indicate the initial shape of the cantilever 40 before the actuation (scale bar of the airay image 2 VO pm. scale bars of a single cantilever 40 on the right 50 mip) Also _, see Si Movie I .

|0104| Tl* inverted additive manufacturing framework, which involves polymerizing incremental elements of material in a build-gap allowed for modulating the composition laycr- by layer to achieve gradations in responses to stimuli FIG. 4A illustrates the approach for «eating integral, molvculaily-ordcred structures 50 with multiple materials Consider printing with monomer l (c.g. K3RP4) to build a suueture 50 Then a change in the composition is desired to monoma 2 (e g R77P1 KO I) To accomplish tins, after printing with monomer I . the build-plate is redacted to release the sample from the PDMS substrate After the temperature is lowcted to ambient, a solvent ( loduerx.' · isopropyl alcohol in 4:1 weight ratio) is introduced to dissolve tiic residual monomers, while not swelling the polymerized structuic llien, the build

?.7 - plate is reset to the doited location and the temperature is raised to dry the build-gap Now. die second monomer is introduced, and the bu¾d process continues

|FI·b| rang *i$ nuidoompoebun proem, a midti-ropoosive robotic aim was buili FIG. 4· •Humes an am 52. which is capable of 2 independent degrees of freedom (A- and Ah «Inch arc responsive to tight and heat respectively The scffncats of the am 52 arc fabricated using

R/7PIRO.I without applying a napKOc Add (pokdomain nematic orientation) They arc tntenoooall> bulky lo ensure they remain entirely non rci pensive and serve a rtmcminl role Joint 53 (him l >. which is designed to be tight responsive i« also fibrtcased uting RZ7PIR0 I and is dwaieiwd by a hooeoiropic dtgmneni tiwough its thin axis ova the entire thickness of 7 Sim Inahaung disjoint with JbSw light lends to bending away Aom dm aclinic source. As seen in the SI Muvic 2. imdUring from dirtereni sides can be used to dove heck and for* actuation at this k*nt by 9. 9 ^* Another joint 54 (Joint 2). was fabricated with the heat responsive R3P1T4 monomer mixture in a bilaycred configuration as illutwd in FIG.4R The «tender eds (W pm Unckneas) of this taint 54 is designed to be normal to that of joint 53 to enable the bending to occui along an orthogonal axis Heating the entire vmicturv elicits a bending behavior along A · ll ^* . This behavior iv luughly analogous so that observed m twisted nematic I .(TP creeled using an analogous composition in Ref In addition tv actuating the touts 53. 54 wing one stimulus at a time, combined application of heat aad light leads to the amulianoou* triggering of manipulation along both 0, and A

|#ia*| FIG. 4A shows a 6, k for modulanng composition uf dm suucdne 5· between layers. FIG. 4B shows a 2-aus robotic amt 51 which is directly 3D printed to tciBae responses indifferent stimuli in the different joints The compositions used in the seucium an shown Joint 53 ½ responsive to tight, by bendrog away thorn the actinic tight doe to its molecular patten Jowl 54 is a bilaycred system, which is responsive to heat Actuation with light (0,) is shown in the top and the thermal acnuiion (A) is shown in the bottom Red dashed lines 55 are used to itiusbate die original location of the fingers of ito arm 52 (scale ban* I mat). Note thu different views used in the panels of FIG. 4B to illume the muhiavial manipulation m response to difTcsent stimuli. Also, sec SI Movie 2

|tlt7| The present dsdoaac also indudtt. m a preferred embodiment, a way to deliver stimulus to individual vends, where the molecular anisotropy has been imprinted In the cate of

-24- Ngbt responsive materials, we envision printing optical waveguides 0 (FIGS. 5 and 4) and fibers amongst tha vondaied liquid crystal pohrmer. For thermally shmulased MT. electrically conductive ebanneb and kxahred Joule hooting dements will be 3D pruned amongst the voxds The idea k to indexahly actuate a 3D structure to eEeh emetgem mechanical and optical

|flM) The goal » to enable new daw» of mittv*j4omcchanical machine» and lab-on-chip devices for microti _l idk maw pul mo·, adaptive optic* esc.

|ilf9) FIGS. 5 and * show optical waveguide» 0. each made of 5 layer» (50 um each) for a total thickness of about 2M)um that have been post cured fis 30 mm at 60"c in vacuum chamber

CONTU SION

|Mlt| A framework for VUMMSCVOUI indexing of the molecular order in 3D freeforms is realized widi magncticaHy-asaistod additive manufacturing of liquid eystallme polymer* The imdertying idea is lo uriN/r a icuncoiaMc magnetic fidd and spatially-resolved irradiation from a digital imcmminrw device to build 3D obfocts in an inverted (honom up) configuration We identify monomer ournpoxiiion». optimized for eotmuHmg dm polymeruamon depth and stimtiluf response, to enable fabrication of heat or light responsive structure* at scale* ranging from dm micro to the macnwacala fhis platform expands the derigs space of mdeculariy -ordered solid* to enable oUcrosauctuial mid composition padNnts m hithano difficult to realize geometries These include, freeform fabrication of bght responsive topographic». heat responsive structure· that generate («mil· curvatures from (Ini geometries and creation of multtresponsivc robutic manipidatnn nidrb rwi be mntridlsri iiimg hm inri'nr light

|tl 11| Xia _k rtah' Thermal lopomivr ream mixture were created using RM257 < 1.4- B«s-|4-(3- acry1oyioxyprop>kwy)b<r¾aoyioxy)-2-«Perl»y1bc»renc ) pk (WiUhinc lochnohqpc*) mixed wHh lrgacurc JW (Ciba specially chemcals) as phocoiahiator. Trouvio 32* 242M-Bo*zotriaaol- i-ylH.^-dHcfi-peotylpheeol (Sigma- Aldrich) as light absorber and Mctbyfhydroquioaoc (Sigma- Aldrich) as inhibitor A range of compositions iluslrmed in Table I were examined light responsive resin mixtures were created ueng RXI257 monomer mixed wi* a/o Ac (4.4-

. 20 - di(6-<acry loxy Hicxyloxy )azobcnzcnc). which was synthesized using the procedure described in Ref lrgaourc 784 (fiba specialty chemicals) as photoinitiator and Methyl rod (2-(4 Di met hvTaminopihenylazo)benzotc acid, 4-DimcthvTaminoazvbcnzcne-2'-caiboxylie acid, Add Rod 2 purchased from Sigmar Aldrich) as light absorber After making the composition, the material was melted and vortex cd It was then dispensed on the PDMS during the lay» -by-layer fabrication of the structures The solvent that was used for removing the monomer during the development of the part at the end of printing process contained T oluene (Fisher Scientific) and Lsopropanol (Fisher scientific) with 4 1 wi

|0112| hahrtctwon System: A commercially available DM!) projector (D9I2IID Vivitck), which was modified to remove the Ϊ L ^G filters was put posed for these expeuments. I¼ position of the build plate was controlled using a one-axis motorized translation stage ( PT I .L1-Z8. Thoilabs) The botinm window was made of a dear acrylic sheet coated with a thin layer of PDMS (Sylgard 184 Dow Coming 184 Silicone Elastomer) In order to control the printing temperature a heating system including a ring disc heater (2U0W. McMastcr). temperature conuollei iPXR », huji Electric). thermocouple* (5SRTC- IT-J-30-36. Omega) and thermometer (HH8f ⁾ 2U. Omega) was built. Permanent Neodymium magnets were purchased from k&J Magnetics and mounted on a motorized rotation stage fPRM l/8, Thnilab*) in order to control the direction of magnetic field

|0I13| I'miimy: method. Fust. A 3D niodd of the desired structure was designed using Solidwnrkx < Dassault S> stuns) and taved in <tl formal llM.fi, the JD model was sliced into black and white 2D patterns of the cross section using sheer software (CrcationWorkshops) These patterns were used later to photopolvmcnze the cross section at each layer Within each layer of the structure, region» that have dilTcicnl molecular alignment were placed m difTcrcnt layers in the C AD model in order to produce different patterns after the slicing step. A covers! ip (build plate) was spin-coated with tdvamidc (DuPont) to achieve sufficient adhesion between the cured material and the covet slip If needed it can also be used rubbed in suitable directions to impose the alignment on m exogens close to the build plate Once die covcrsiip was attached to the platfoim it was moved to the desired location (bin Id-gap) close to the PDMS I ^“ he cell was then heated to the desired temperaturo that falls within the nematic phase range of the monomer. The molten monomer mixture was then introduced into die build-gap to build the subsequent layers A 0 3 T magnetic field was introduced by using two Ncodvmium pcimanent magnets

- to (grade N<2, KAJ Magnetics) In order to achieve the programmed orientation induced by magnetic field, a 5 min dwell time was induced before polymerization I be dwell time provides enough time for the mesogens u> rotate and align parallel with the magnetic field Then. the desired 2D pattern was exposed The exposure period and intensity were derived from the working curve. For light responsive materials, a 495 nm long pass fillet was used The printing process amtinued by lifting the platform, rotating the magnetic field (if required) and exposing 2D patterns repeatedly When all the layers were polymerized and the 31) object was completed, the build plate moved up and the printed structure was removed from the printer. For the final development the sample was unmoved in the vv!vcnt (Toluene and IRL 4 I ) fur 2-5 min Finally, it was dried in a vacuum chamber for 2-3 min The final product generally required post curing process which wax executed by exposing - 20 mW cm" 1 i V light (green light for light responsive materials) for about 30 minutes or heating the sample up to 7< C for I hour

|0114| Mrawrrrm'nf of u nr buy i wnvv The curing depth were measured for the \ aiiety of photonic energy intensity and material compositions m Tablet Bv controlling the grayscale values in the 2D patterns which were projected control uvci the light intensity was achieved Direct measurements of intensity using a power meter was performed In order to measure the polymerization depth, the build plate was placed - 2 mm from the PDMS and the whole gap was filled with the monomer. Bv exposing square patterns with different intensities, the poly met i zaii on started ft uni the POMS surface up to some level bdow the build plate Squares with higher intensity (brighter patterns) cured up to higher levels Measuring the thickness of these squares by a digital micrometer yielded polymerization depth for the respected conditions This data was used to populate the working curses, which arc illustrated m HG. 2.

Supporting Information

10115] The Supporting information is available I tee of charge via the Internet at http /pubs act org

|0I I6| Additional figures of the setup. 2D patterns and actuation of basket ! ike geometries (PDF)

|0117| Light actuation of overhanging cantilevers (AVI) xi pilt| Applying UV light irradiating from diHereai tide* in order to drive the robotic arm back andfbnkfAX'h pi lt| Vmrimrt Mahcula PMKnmgn 3-Pimcminnal tmfoflM PI¾N Mohsee Ttiifivi. Taykw II. Warcaad M Ravi Shaakte * pi2l| FIG. 7 «bow* * profaned 3D printer setup If of to pmeat duckauc and it» compoooeis comprising a magnet 71. build plate 72. PDMS subsume 71. hut stage 74 and DLP propeckN 75

P122| PO. · tows black and white 2D paacm* 74 used for fabricating the bi layer basket of FIG. JA. The a/imulhal mnkcwlai urientaUon wax encoded by breaking the ring 71 into 16 deficient segment* and S dflhnat molecular alignment». Potentially. the accuracy can be Increased by atgawating be pattern tnto smaNcr sccDons. The magnetic fteld direction far each pattern (two segments) wt noted ia to inset* ⁷ 6

PI23| nUSL f A *· show ovcrcunamic drixna «anaformabon of sauctures of the basket- kite goomcete» If. 11 due to thermal actuation A ranige of ovencurvatiae value» be accessed by varying die radius of be a/imuthally -oriented paaern in the prior Hat state (scale bars ■ l mmX

PI24| FKL If A show» a tivee -dimensional CAD model 47 and FIG. If· show» patterns *f u»od for making the array 45 of overhang»·}; cantilevers 40

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