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1  (GH13), have their chemical steps concealed kinetically.
2 major by-product) both thermodynamically and kinetically.
3 h thousands of free monomers and ending with kinetically accessible and thermodynamically stable amyl
4                                 Arguing that kinetically accessible metastable structures might be mo
5 opentadienyl cationic intermediates are more kinetically accessible, as well as more thermodynamicall
6 ion to ensure that the intended structure is kinetically accessible.
7 y inert compounds) or pseudo-proton sponges (kinetically active) are discussed.
8 fluorescent proteins through single pores is kinetically analysed using massively parallel optical re
9 ctivity over C-H bond activation is achieved kinetically and allows for the generation of functionali
10                                 Complex 2 is kinetically and catalytically competent to perform the e
11    Our recent report of Y356* formation in a kinetically and chemically competent fashion in the reac
12 2) The reductive half-reaction of 2-KPCC was kinetically and spectroscopically similar to that of a t
13 rently, only prokaryotic orthologs have been kinetically and structurally characterized.
14           Seven catalytic intermediates were kinetically and structurally resolved in the crystalline
15 ds have been designed to stabilize otherwise kinetically and thermodynamically disfavored 6-membered
16 f 1,2,4-oxadiazolidin-5-ones is favored both kinetically and thermodynamically independently of the s
17 , to show that alternative conformations are kinetically and thermodynamically more readily accessibl
18 ding to 3-aminopyrroles was shown to be both kinetically and thermodynamically most favorable.
19 , which showed that in all cases C-attack is kinetically and thermodynamically preferred over O-attac
20 e, subsequently deactivating the 1,2-H shift kinetically and thermodynamically.
21 ous time and length scales and show that the kinetically arrested metastable multi-droplet state is a
22                               We show that a kinetically arrested state can be induced by randomly pi
23  a flowing and liquid crystalline state to a kinetically arrested state.
24 est that HDA formation is a consequence of a kinetically arrested transformation between low-density
25 gh energy barrier to colloidal rearrangement kinetically arrests the onion-like structure formed by h
26 , ketene, ethanol, acetylene, and ethane are kinetically blocked.
27  CHOH to form CH4 while C2 (C3) pathways are kinetically blocked; (2) at neutral pH, the C1 and C2 (C
28             We find that shape is determined kinetically, but many reactions between different phases
29 as been extensively studied structurally and kinetically, but several key steps following phosphodies
30  of carbonate diesters has been investigated kinetically by applying the LFER equation log k = sf(Ef
31 (+) gradient ([Formula: see text]) functions kinetically by decreasing the K(m) for influx 50- to 100
32  DNA binder, and its unbinding is controlled kinetically by molecular stripping from the DNA induced
33 d thermodynamically by the nucleation, while kinetically by the enhanced Zn adsorption and O diffusio
34 aged disulfide structures, which can then be kinetically captured upon sulfur extrusion at room tempe
35 os have led to efforts that made it the most kinetically characterized enzyme, yet these studies focu
36 catalytic fragment of p261 (p261N), which we kinetically characterized in our earlier studies, the pr
37       The systems were thermodynamically and kinetically characterized regarding their 1:1 binding pr
38 onships of these loops, here we produced and kinetically characterized several variants in which four
39  TS of hPNMT were designed, synthesized, and kinetically characterized.
40 ron-rich and poor monomers are prepared that kinetically coassemble through a temperature-controlled
41                Gastric and ileal chymes were kinetically collected over the postprandial period.
42 niques show that high protein concentrations kinetically compartmentalize the flagellum: Within milli
43          The amyloidogenic aggregation would kinetically compete with the process of membrane permeat
44 esulting in a pre-organized ligand shell for kinetically competent and error-free photo-assembly of t
45  because of the historical unavailability of kinetically competent assays with physiologically releva
46  of the leaving group and therefore the most kinetically competent natural substrates.
47 synthesize new or metastable complex oxides, kinetically competent reactions with lower initial energ
48 he substrate complexes are catalytically and kinetically competent to be intermediates in allylic sub
49 terized, and determined to be chemically and kinetically competent to undergo the proposed elementary
50 complexes were shown to be catalytically and kinetically competent.
51 f supramolecular self-assembly by connected, kinetically competing enzymatic reactions.
52 gen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multis
53 uggest that the observed quenched states are kinetically consistent with either two or one bound OCPs
54 n states from that found in the final MOF-to kinetically control self-assembly.
55  nucleation domain may enable engineering of kinetically controllable self-assembling 2D macromolecul
56 ses synthetic challenges such as the unusual kinetically controlled (1 -> 2)-beta-oligomannan domain,
57    We demonstrate that the ZTP riboswitch is kinetically controlled and that its activation is favore
58 T becomes less prominent and eventually gets kinetically controlled at room temperature.
59 d with a characteristic time of 36 ps, being kinetically controlled by energy transfer from the long-
60 tegy that significantly expands the scope of kinetically controlled catalytic Z- and E-selective olef
61 med that O attack is generally favored under kinetically controlled conditions, whereas C attack is f
62 rminal deoxynucleotidyl transferase (TdT) in kinetically controlled conditions.
63                    It is used to carry out a kinetically controlled covalent immobilisation of trypta
64 dominant paradigm is that it is a product of kinetically controlled cracking of long-chain hydrocarbo
65                        The first examples of kinetically controlled cross-metathesis reactions that g
66       Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks
67 rom the constituent amino acid subunits with kinetically controlled diastereoselective introduction o
68                     Illustrative examples of kinetically controlled E-selective cross-metathesis and
69                        We demonstrate that a kinetically controlled heme-dependent metabolite switch
70               Selectivity is attributed to a kinetically controlled process where the rate of monomer
71  observed self-sorting is a symmetry-driven, kinetically controlled process.
72 ctive for the C5-borylated 1,2-azaborine via kinetically controlled processes.
73 [1,5]H-shift (2 --> 4), thereby favoring the kinetically controlled product (3a-3j) as anticipated.
74 plex due to spontaneous symmetry breaking or kinetically controlled random assembly formation.
75 es with relative energetics that support the kinetically controlled reaction pathway are preferred, m
76 state chemistry, requires the development of kinetically controlled reaction pathways.
77                                       In the kinetically controlled reaction, only the formation of t
78 ective and, according to DFT calculations, a kinetically controlled reaction.
79 ur detailed studies on thermodynamically and kinetically controlled supramolecular polymerization of
80 tracene analogue with five-membered rings is kinetically controlled while an "expected" product with
81  to dehydrate at all pH values, the presumed kinetically controlled yield of 17alpha-TBOH photohydrat
82                                              Kinetically controlled Z-selective RCM reactions have be
83  while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically d
84                  These nanomaterials exhibit kinetically controlled, irreversible CO(2) uptake profil
85                We find that NPL formation is kinetically controlled, whereas thermodynamic parameter
86                 As a result, its presence is kinetically controlled, which gives the associated supra
87 electrolyte, and that ionic transport can be kinetically controlled.
88 provide evidence in support of a sterically (kinetically) controlled mechanism, whereby gauche intera
89                                  We design a kinetically-controlled regime of colloidal synthesis to
90        The ternary compound is formed due to kinetically-controlled synthesis conditions and is analy
91 g ribosome can both physically associate and kinetically coordinate with RNA polymerase (RNAP)(3-11),
92 of the tyrosine (Y215F, Y215H) were analyzed kinetically, crystallographically and by molecular dynam
93 hromophore and the protein scaffold are more kinetically decoupled than in other microbial rhodopsins
94                               Several of the kinetically defined steps of BRD4 in this study are prop
95 nomeric to a fibrillar state via a series of kinetically defined steps.
96 on by acting at a minimum of three different kinetically defined steps.
97 minimization tools when multiple structures, kinetically determined structures, or complex RNA-RNA an
98 ate allosteric model and instead is probably kinetically determined.
99  changes in surface coverage for each set of kinetically differentiable species.
100      The mismatch modification allows one to kinetically differentiate initiation versus propagation
101         These features imply a more dynamic, kinetically discontinuous replication process, wherein c
102                           The success of the kinetically disfavored 5-endo cyclization was attributed
103 , CH2O and HF, with the latter channel being kinetically disfavored.
104                                     Here, we kinetically dissect Sec-dependent translocation by monit
105                           These mice develop kinetically distinct autoimmune progression, with approx
106  SBACs arise from the ordered arrangement of kinetically distinct bipolar cell inputs.
107 ate constants for ATPS formation fall into 3 kinetically distinct categories that are directly visual
108 -biased opioid agonist, c) Identification of kinetically distinct conformational states to be used fo
109 half sites, p53/DNA complexes existed in two kinetically distinct populations.
110 f hydrogel networks by utilizing mixtures of kinetically distinct reversible covalent crosslinks.
111 ore, when relaxed, myosin partition into two kinetically distinct subpopulations: a faster-hydrolyzin
112               EVS activation engages several kinetically distinct synaptic processes that profoundly
113 me boutons, neurons or sources provide these kinetically distinct types of inhibition was not known.
114  provides mechanical force essential for all kinetically distinguishable forms of endocytosis at syna
115 r pH values, an acid-catalyzed mechanism was kinetically dominant and, last, a water reaction was pos
116           The oxidative electron transfer is kinetically dominant as a result of the unusually strong
117 ansfer (CPET) must overcome competing, often kinetically dominant hydrogen evolution.
118 react via three distinct mechanisms with the kinetically dominant mechanism being dependent on the pH
119 tein kinase (vPK), encoded by a gene that is kinetically downstream of the lytic switch, sustains exp
120                  In this study, we show that kinetically driven processes in a system of rapidly decr
121 ransition there is a boost in activity for a kinetically driven reaction, ethylene epoxidation, givin
122 scape of transcription initiation suggests a kinetically driven regulation of mitochondrial transcrip
123 escape from thermodynamic equilibrium toward kinetically driven states is a hallmark of life and its
124  true molecularity, and hence the associated kinetically effective nucleus (KEN), for nanoparticle fo
125 ic receptor dimer rearrangements and that is kinetically embedded between receptor-G protein complex
126                                NKTR-214 is a kinetically-engineered IL-2 receptor betagamma (IL-2Rbet
127 r weight and oligomeric carboxylic acids are kinetically equivalent at accelerating this isomerizatio
128 eduction of 1.[O] to P(III) phosphetane 1 is kinetically fast under conditions of catalysis; (2) phos
129 nt publications, Li dendrite growth is still kinetically favorable and it remains a severe safety con
130 thode, dislocation-mediated ion diffusion is kinetically favorable at low SOC and planar diffusion al
131          It provides a thermodynamically and kinetically favorable means to form aoQMs, independent o
132 y functional theory results support that the kinetically favorable mechanism for the formation of iso
133 rast, for the reaction of free monomers, the kinetically favorable reaction pathway is the cross-coup
134 ent largely affected which reactive site was kinetically favorable.
135 vity for anti-Markovnikov oxidation over the kinetically favored alkene epoxidation by trapping high-
136 ion of the dipeptide yielded the alternative kinetically favored benzodiazepine scaffold.
137 gen, and that surface oxygen release is then kinetically favored during charging.
138 oviding synthetically useful quantities of a kinetically favored olefin isomer.
139 proton back leakage through the D-channel is kinetically favored over proton pumping due to the loss
140 gy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with t
141  is preceded by Cu(II) binding in a separate kinetically favored site that is distinct from the activ
142  BNC, but that the former (i.e., pumping) is kinetically favored whereas the latter (i.e., transfer o
143      Then, the CO release from 1((II))-CO is kinetically favored, facilitating the catalysis.
144 ls, as the reactions operate exclusively via kinetically favourable "normal"-sized cyclic transition
145                                  To identify kinetically favourable substrates we performed a GSK3 su
146 trapping of MGO by Cys residues is initially kinetically favourable.
147 n expressed sequence tag library), evaluated kinetically for its substrate/inhibitor profile and asse
148 howed outstanding selectivity (>98%) for the kinetically hindered 4e(-)/4H(+) reduction of O(2) to H(
149 NA interaction might be transduced by RNA to kinetically impact a second.
150  populations, we can "visualize" a series of kinetically important intermediates, track the kinetics
151 achieving the magnitude of the IPCC's EFs is kinetically improbable in most river systems.
152 n ionophore-based polymeric membranes can be kinetically improved by several orders of magnitude in c
153 nclude that the MPST1 and MPST2 isoforms are kinetically indistinguishable and that thioredoxin modul
154 (4) m(-1) s(-1)), and both Cys residues were kinetically indistinguishable.
155  stable (log K(MnL) = 19.01, pMn = 9.27) and kinetically inert complex with Mn(II) with respect to tr
156 al nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (k
157 mer units are attached to the template using kinetically inert covalent bonds it should be possible t
158                   The chiral resolution of a kinetically inert molecular ruby [Cr(dqp)(2)](3+) (1, dq
159                     The activation of such a kinetically inert molecule was achieved by the use of bi
160  The C-H bonds of methane are generally more kinetically inert than those of other hydrocarbons, reac
161 tions, at least at the micrometer scale, are kinetically influenced by concomitant solvent motion tha
162                                     Although kinetically invisible, the second deoxygenation stage is
163 r containing thermodynamically stable whilst kinetically labile coordination complex to address this
164 import is mediated by Kap122 plus redundant, kinetically less efficient import pathways.
165 of acetylene oligomerization, is shown to be kinetically less favorable.
166  water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in th
167 n, using an artificial electron acceptor, is kinetically limited by diffusional intermolecular electr
168 ntial in a dimensionless form, which unifies kinetically limited evaporation under different working
169    We experimentally realized and elucidated kinetically limited evaporation where the molecular gas
170 tivity for the CO(2) reduction reaction in a kinetically limited regime with near zero overpotential
171 ggested that the regeneration process may be kinetically limited.
172 Na- and Cs-MER show non-Type I isotherms and kinetically-limited CO(2) adsorption and delivery of pur
173 uce a water residence time dependence, which kinetically limits the extent of denitrification and nit
174 it has not been possible to deconvolve these kinetically linked processes to determine the earliest c
175                         Halide guests can be kinetically locked within the structure by oxidation of
176 AM enzymes, the slow radical initiation step kinetically masks the subsequent steps, making it imposs
177 bay-positions, revealed that these PBIs form kinetically metastable H-aggregates, which can be transf
178 y ice has a proton-disordered phase which is kinetically metastable, unable to reach, spontaneously,
179  oxidative degradation of wolfberry pulp was kinetically monitored using model-free and model-based a
180 -)/4H(+) reduction of O(2) to H(2)O over the kinetically more accessible 2e(-)/2H(+) reduction to H(2
181 he surface, which results in a state that is kinetically more stable with larger optical birefringenc
182  stable than the ScRad51 ones because of the kinetically much reduced nucleation step.
183   The purpose of this study is to assess the kinetically optimal pathways in relation to the formatio
184 ether their reactions with electrophiles are kinetically or thermodynamically controlled and whether
185          Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into
186 pentyl)benzene, intramolecular C-H amination kinetically outcompetes formation of the corresponding t
187 increases the fraction of folded proteins by kinetically partitioning more molecules through on-pathw
188 NDOR probes to test, detect, and corroborate kinetically predicted trends in active site reactivity a
189              Polymerization to cis-isomer is kinetically preferred at low temperature, not only in th
190 t the metal with each propagating step and a kinetically preferred diastereomeric relationship betwee
191 re possible for the detectable (THFA)(2) : a kinetically preferred dimer bound by feeble interactions
192 l ribozyme unfolding cycles lead back to the kinetically preferred misfolded conformation and are not
193  indicating the faster reducing agent formed kinetically preferred nanowires.
194 ion leading to the formation of sultines was kinetically preferred over the loss of sulfur dioxide le
195 rotocols offer a new ability to both profile kinetically privileged sensors (KPSs) of RES at a system
196 nly generate Z-olefins selectively, but also kinetically produce E-olefins, a previously unmet challe
197 ified metabolites (142 reliably detected, 46 kinetically profiled) selected from >35 metabolic pathwa
198 hat evaporative helium cooling is capable of kinetically quenching the nonequilibrium tetramer system
199                                Compound 3 is kinetically reactive and reacts in the microsecond time
200 involved enzymes indicates that Roseobacters kinetically regulate the DMSP demethylation pathway to e
201  suggest that TM mechanosensitivity utilizes kinetically, regulatory and functionally distinct pressu
202 d mechanistic studies provided support for a kinetically relevant C-C scission, and a well-defined or
203 B(2-)*, O(2)(*-), and H(2)O(2)) that are not kinetically relevant for other compounds.
204 lently bound alkoxides form C-C bonds in the kinetically relevant step for dimerization turnovers on
205 hat the oxidative addition is not the single kinetically relevant step in different cross-coupling re
206 direct involvement of reactive oxygen in the kinetically relevant step leads to more effective CH4 tu
207 tial C-H bond activation remains as the sole kinetically relevant step on Ni-Co, Ni, and Co clusters,
208 se have contributed to the alkylation in the kinetically relevant step.
209 and analyzed by the finite element method to kinetically resolve all steps of the ECadsCmag mechanism
210 fluorescence polarization (FP) spectroscopy, kinetically resolves the dissociation of detergents from
211 erall reaction that is thermodynamically and kinetically reversible.
212 rinciple is to design monomer species having kinetically selected molecular recognition in the struct
213 ameters differ by less than an angstrom show kinetically selective organic liquid reverse osmosis.
214 ts demonstrate a general strategy to control kinetically self-assembly beyond thermodynamic products
215          In this study, we have introduced a kinetically sensitive dual-frequency designer waveform i
216                            This material can kinetically separate ethylene from ethane with an unprec
217                    We clearly identify three kinetically separated states (an unbound state, an encou
218 d it is expected that this species should be kinetically short-lived.
219 ions, and we outline a procedure to identify kinetically significant transition states and adsorbed i
220 e that C-H activation is both reversible and kinetically significant.
221 binding sites of plasmin(ogen) and is only a kinetically slow plasmin inhibitor.
222 y remain in an off-state long enough for the kinetically slower epigenetic silencing mechanisms to ac
223        However, this reaction is known to be kinetically sluggish and proceeds at rather high overpot
224     The oxygen evolution reaction (OER) is a kinetically sluggish anodic reaction and requires a larg
225 -abundant electrocatalysts to accelerate the kinetically sluggish hydrogen and oxygen evolution react
226 ure energy demands, but often limited by the kinetically sluggish hydrogen evolution reaction (HER) o
227 as employed to identify small molecules that kinetically stabilize LCs.
228 rugs, bind directly to tubulin subunits and "kinetically stabilize" microtubules, suppressing the cha
229  favorable core-shell Ag@Au nanostructure is kinetically stabilized by the intermediate Ag20 shell, p
230 rotection strategy that provided access to a kinetically stabilized complex with mixed O(2-)/S(2-) li
231 C-H functionalization intermediates, and not kinetically stabilized model complexes, these experiment
232                                  We produced kinetically stabilized Rous sarcoma virus (RSV) intasome
233 udies indicate that the compound is far from kinetically stable ( intramolecular rearrangements).
234  soluble domain of Atp7a), thus leading to a kinetically stable adduct that has been structurally cha
235 able air-stable dimeric dopant can result in kinetically stable and efficient n-doping of host semico
236 whereas non-amyloidogenic LC dimers are more kinetically stable and resistant to endoproteolysis.
237 cesium lead iodide (gamma-CsPbI(3)) that are kinetically stable at room temperature.
238 quely situated in the periodic table to form kinetically stable compounds often with chemically stabl
239                             The systems were kinetically stable for at least 3 weeks at 4 degrees C.
240 ns can rearrange following electrospray into kinetically stable gas-phase conformations).
241 ion and in the dark results in thermally and kinetically stable glasses.
242             It has been established that the kinetically stable hypervalent iodine form (I-CF(3)) of
243 zing the formation of structurally distinct, kinetically stable integrase-DNA product complexes, depe
244    Under these conditions, the compounds are kinetically stable over long time periods (>100 days).
245  have been employed to describe a variety of kinetically stable polyionic molecular species that are
246 nely provides structural characterization of kinetically stable pre-catalysts and intermediates, eluc
247 l flow readily unfolds thermodynamically and kinetically stable proteins, exposing previously sequest
248 ing; both modern RNases H evolved to be more kinetically stable than their most recent common ancesto
249 teins' isolated N-terminal domains were less kinetically stable than their respective C-terminal doma
250 r reduction by one electron path, leaving it kinetically stable to the vast majority of organic cellu
251        The chiral guest-included helicate is kinetically stable, existing as a mixture of right- and
252  existence of these "cross" supermicelles as kinetically stable, micron-size colloidally stable struc
253              Though vaterite is at best only kinetically stable, that stability is tunable, as vateri
254 catalyze peptide ligation, directly coupling kinetically stable-but energy-rich-alpha-amidonitriles t
255 but that in PARN-mutant cells hTR maturation kinetically stalls and unprocessed precursors are degrad
256 celerates dissociation of unloaded bonds and kinetically strengthens strained bonds.
257                 Polar environments lead to a kinetically stronger, shorter, and more polar bond betwe
258    We have investigated immunochemically and kinetically the occurrence of CatC and its proform in hu
259 other enzymatic processes that are similarly kinetically-, thermodynamically-, and/or stability-limit
260  and mass evaporation effects are controlled kinetically/thermodynamically.
261 roximately 0.1 s, a transition occurs from a kinetically to a largely thermodynamically controlled di
262 rdinate expression of c-MYC, which is linked kinetically to that of PRC in response to multiple stres
263 m at the interface, opening a novel route to kinetically trap the liquids in non-equilibrium shapes.
264 In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) st
265 rcent of all transmembrane proteins exist in kinetically trapped aggregation-prone states that have b
266 namically stable beta-structures and then to kinetically trapped alpha-structures.
267                                  Producing a kinetically trapped analog of I(T) by deleting the N-ter
268               Stable liposomes are typically kinetically trapped and are not prone to exchanging diac
269 nected structures of two immiscible liquids, kinetically trapped by colloidal particles that are irre
270        Because of the irreversibility of the kinetically trapped clusters, we found that the behavior
271 led transiently, or assembled permanently in kinetically trapped clusters.
272 ture, T (gel) , the proteins assemble into a kinetically trapped gel state that arrests ATPS formatio
273 was added at once, the material would end up kinetically trapped in a local minimum.
274         Thus, the monomers of these PBIs are kinetically trapped in conformationally restricted state
275 resent work, the structural interrogation of kinetically trapped intermediates of cyt c was performed
276 ucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level.
277   The example reported here illustrates that kinetically trapped products may facilitate high yields
278 e observed nonclassical fullerene could be a kinetically trapped species derived from the recently re
279  the conformational search, we find that the kinetically trapped species have a trans-trans configura
280                                            A kinetically trapped state A is reached upon cooling to 7
281 dicate that nucleation starts from a central kinetically trapped state Agg 1 and involves the reorgan
282 phase being out of equilibrium, in a surface kinetically trapped state.
283 n of a second and propagated into long-lived kinetically trapped states (>=90-mer).
284        We show here that copolymerization of kinetically trapped states of one PBI with seeds of anot
285 Our results demonstrate how GB phases can be kinetically trapped, enabling atomic-scale room-temperat
286  high-energy surfaces for catalysis that are kinetically trapped.
287 ic equilibrium, instead yielding mixtures of kinetically-trapped species.
288                Biological structures rely on kinetically tuned charge transfer reactions for energy c
289              However, the protein folds in a kinetically two-state manner and is moderately stable at
290                                      It is a kinetically unfavorable process that is templated in the
291 wer excited state where electron transfer is kinetically unfavorable.
292 ), multi-protein complexes that catalyse the kinetically unfavourable formation of new microtubules i
293 ergy and selectively producing a desired but kinetically unfavourable product for the important carbo
294 ata suggest that amyloidogenic LC dimers are kinetically unstable (unfold faster) and are thus suscep
295 ab), using a novel assay, which is validated kinetically using the nitrocefin reporter assay and in s
296 f the most stable tris-peroxide is the least kinetically viable and is not observed experimentally.
297 hat direct, anhydrous Cs(+)-K(+) exchange is kinetically viable and leads to the formation of phase-s
298 der thermodynamic control and can be trapped kinetically when desired are key to creating complex sys
299 nd growth process both thermodynamically and kinetically, which contributed to the morphological evol
300 s barrier leads to repriming, which competes kinetically with TLS.

 
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