Role of Molecular Dipoles in Charge Transport across Large Area Molecular Junctions Delineated Using Isomorphic Self-Assembled Monolayers

Delineating the role of dipoles in large area junctions that are based on self-assembled monolayers (SAMs) is challenging due to molecular tilt, surface defects, and interchain coupling among other features. To mitigate SAM-based effects in study of dipoles, we investigated tunneling rates across carboranesisostructural molecules that orient along the surface normal on Au (but bear different dipole moments) without changing the thickness, packing density, or morphology of the SAM. Using the Au-SAM//Ga₂O₃-EGaIn junction (where “//” = physisorption, “–” = chemisorption, and EGaIn is eutectic gallium–indium), we observe that molecules with dipole moments oriented along the surface normal (with dipole moment, <i>p</i> = 4.1D for both M9 and 1O2) gave lower currents than when the dipole is orthogonal (<i>p</i> = 1.1 D, M1) at ±0.5 V applied bias. Similarly, from transition voltage spectroscopy, the transition voltages, <i>V</i>_T (volt), are significantly different. (0.5, 0.43, and 0.4 V for M1, M9, and 1O2, respectively). We infer that the magnitude and direction of a dipole moments significantly affect the rate of charge transport across large area junctions with Δ log|J| ≅ 0.4 per Debye. This difference is largely due to effect of the dipole moment on the molecule-electrode coupling strength, Γ, hence effect of dipoles is likely to manifest in the contact resistance, <i>J</i>_o, although in conformational flexible molecules field-induced effects are expected

Structure of Aqueous Water Films on Textured −OH-Terminated Self-Assembled Monolayers

We report the thickness and interfacial molecular structure of thin (1–3 nm) aqueous films supported on hydroxyl-terminated self-assembled monolayers over a silver substrate. The water film structure is studied as a function of varying the monolayer’s methylene chain lengths. Analysis techniques include ellipsometry, contact angle, and polarization modulation reflection adsorption infrared spectroscopy. The aqueous film thicknesses follow 4-mercaptobutanol (4-MBU) > 11-mercaptoundecanol (11-MUD) > 6-mercaptohexanol (6-MHE) > 9-mercaptononanol (9-MNO). Water contact angle measurements across the same surfaces are very similar; however, vibrational spectroscopic analysis of the films shows that intermolecular bonding patterns of D₂O are significantly different from those of bulk D₂O. This evokes unique interfacial molecular architectures for each of these films. The structural differences depend on the nature of the SAM structure and resulting water–SAM interactions, which are evident from PM-IRRAS data. Spectroscopic peak intensity ratios of ν­(O–D) modes suggest more asymmetric hydrogen-bonded D₂O character near 9-MNO surfaces, whereas 4-MDU, 6-MHE, and 11-MUD surfaces exhibit increasingly symmetric hydrogen-bonded D₂O character. From this, we propose a model for film structure

Limits to the Effect of Substrate Roughness or Smoothness on the Odd–Even Effect in Wetting Properties of <i>n</i>‑Alkanethiolate Monolayers

This study investigates the effect of roughness on interfacial properties of an <i>n</i>-alkanethiolate self-assembled monolayer (SAM) and uses hydrophobicity to demonstrate the existence of upper and lower limits. This article also sheds light on the origin of the previously unexplained gradual increase in contact angles with increases in the size of the molecule making the SAM. We prepared Au surfaces with a root-mean-square (RMS) roughness of ∼0.2–0.5 nm and compared the wetting properties of <i>n</i>-alkanethiolate (C₁₀–C₁₆) SAMs fabricated on these surfaces. Static contact angles, θ_s, formed between the SAM and water, diethylene glycol, and hexadecane showed an odd–even effect irrespective of the solvent properties. The average differences in subsequent SAM^E and SAM^O are Δθ_{s|<i>n </i> – (<i>n</i>+1)|} ≈ 1.7° (<i>n</i> = even) and Δθ_{s|<i>n </i>– (<i>n</i>+1)|} ≈ 3.1° (<i>n</i> = odd). A gradual increase in θ_s with increasing length of the molecule was observed, with values ranging from water 104.7–110.7° (overall Δθ_s = 6.0° while for the evens Δθ_s^E = 4.4° and odds Δθ_s^O = 3.5°) to diethylene glycol 72.9–80.4° (overall Δθ_s = 7.5° while for the evens Δθ_s^E = 2.9° and odds Δθ_s^O = 2.4°) and hexadecane 40.4–49.4° (overall Δθ_s = 9.0° while for the evens Δθ_s^E = 3.7° and odds Δθ_s^O = 2.1°). This article establishes that the gradual increase in θ_s with increasing molecular size in SAMs is due to asymmetry in the zigzag oscillation in the odd–even effect. Comparison of the magnitude and proportion differences in this asymmetry allows us to establish the reduction in interfacial dispersive forces, due to increasing SAM crystallinity with increasing molecular size, as the origin of this asymmetry. By comparing the dependence of θ_s on surface roughness we infer that (i) RMS roughness ≈ 1 nm is a theoretical limit beyond which the odd–even effect cannot be observed and (ii) on a hypothetically flat surface the maximum difference in hydrophobicity, as expressed in θ_s, is ∼3°

Table_7_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Image_1_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.jpeg

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Table_14_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Table_6_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Table_5_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Table_1_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p

Table_12_Comprehensive identification and analysis of circRNAs during hickory (Carya cathayensis Sarg.) flower bud differentiation.xlsx

Flower bud differentiation represents a crucial transition from vegetative growth to reproductive development. Carya cathayensis (hickory) is an important economic species in China, with a long juvenile period that hinders its commercial development. In recent years, circular RNAs (circRNAs) have been widely studied and identified as sponges for miRNA regulation of mRNA expression. However, little is known regarding the role of circRNAs in flower buds. In this study, we sequenced circRNAs at three developmental stages (undifferentiated, differentiating, and fully differentiated) in both female and male buds. A total of 6,931 circRNAs were identified in the three developmental stages and 4,449 and 2,209 circRNAs were differentially expressed in female and male buds, respectively. Gene ontology demonstrated that many circRNA host genes participated in various processes, for example, cellular and intracellular pH regulation. Function annotation identified 46 differentially expressed circRNAs involved in flowering regulation, with 28 circRNAs found only in female buds, 4 found only in male buds, and 11 found in both female and male buds. A circRNA-miRNA-mRNA network was predicted based on 13 flowering-related circRNAs and their seven putative interacting miRNAs to describe the regulatory mechanism. Our preliminary results demonstrated a potential involvement of circRNA in bud differentiation. They provided a preliminary theoretical basis for how circRNA might participate in flower development in hickory, perhaps in woody plants.</p