Women’s access to and control over land in the current land administration system in two rural kebeles in Ada’a Woreda of Oromia Region

The study is designed to explore the status of rural women in access to and control over land in the current land administration system in two rural Kebeles in East Shewa Zone Ada’a Woreda of Oromia region on smallholder farmers’ landholding registration. The Ormia National Regional State Rural Land Administration and Use Proclamation and its implementation procedure are examined from a gender perspective in terms of ensuring rural women’s land holding rights and control they have over land. Historical overview on the land question in Ethiopia revealed that tenure systems evolved through historical periods. Land remained under men’s control throughout history and men’s control over land was strengthened by the rural land reform carried out by the Derg. This tenure reform applied rural land distribution using households as unit for rural land allocation and women were disadvantaged as most rural households were headed by men. The Oromia rural land proclamation is not discriminatory on basis of sex. However, policy gaps are evident in addressing women specific issues such as issues of FHHs and women under polygamous marriages. Gaps also exist between policy and implementation. Customary laws and practices have serious impacts on women’s land rights at the level of implementation. The research applied both quantitative and qualitative methods in view of feminist research methodology to properly address issues from a gender perspective. Survey of 318 households was conducted administering questionnaires in the quantitative method. The qualitative method applied was interviews with relevant Woreda office and Kebele LACs, focus group discussions with rural women, case stories and observation. Triangulation method is applied in data collection, data presentation and in analysis of findings. Study findings reveal that women’s access rights to land is less equal than legally provided. This study evidences gaps between policy and implementation. Customary laws and traditional practices generally have impacts on land access rights of single/unmarried, divorced, widowed women and on access rights of women in polygamous marriages. Women’s control over land is not efficiently addressed by the regional rural land policy. This is a significant policy drawback as women’s equal rights on land could not be achieved without gaining control over land. The land administration system in general and the land registration process in particular has not considered women’s participation in community activities and decision-making. Women are not represented in LACs and Sub-Committees in both Kebeles. Study findings indicate absence of autonomous institution as gap in addressing women’s issues in the land administration system. This study also revealed loose linkages between the rural land policy and other regional legislations like the regional family law which provides women’s equal rights on land in marriage and on its abandonment. This study forwards recommendation to address gender gaps identified to ensure women’s equal access to and control over land in the study area. The Oromia rural land proclamation needs revision from a gender perspective to address women’s specific issues and the land administration system should consider women’s participation in the process, their contribution to the system as well as their equal benefits from policy outcomes

Transferability in Machine Learning for Electronic Structure via the Molecular Orbital Basis

We present a machine learning (ML) method for predicting electronic structure correlation energies using Hartree–Fock input. The total correlation energy is expressed in terms of individual and pair contributions from occupied molecular orbitals, and Gaussian process regression is used to predict these contributions from a feature set that is based on molecular orbital properties, such as Fock, Coulomb, and exchange matrix elements. With the aim of maximizing transferability across chemical systems and compactness of the feature set, we avoid the usual specification of ML features in terms of atom- or geometry-specific information, such atom/element-types, bond-types, or local molecular structure. ML predictions of MP2 and CCSD energies are presented for a range of systems, demonstrating that the method maintains accuracy while providing transferability both within and across chemical families; this includes predictions for molecules with atom-types and elements that are not included in the training set. The method holds promise both in its current form and as a proof-of-principle for the use of ML in the design of generalized density-matrix functionals

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO₂ to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO₂ reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO₂, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO₂, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO₂ substrate

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO₂ to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO₂ reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO₂, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO₂, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO₂ substrate

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO₂ to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO₂ reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO₂, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO₂, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO₂ substrate

Salt Effect Accelerates Site-Selective Cysteine Bioconjugation

Highly efficient and selective chemical reactions are desired. For small molecule chemistry, the reaction rate can be varied by changing the concentration, temperature, and solvent used. In contrast for large biomolecules, the reaction rate is difficult to modify by adjusting these variables because stringent biocompatible reaction conditions are required. Here we show that adding salts can change the <i>rate constant over 4 orders of magnitude</i> for an arylation bioconjugation reaction between a cysteine residue within a four-residue sequence (π-clamp) and a perfluoroaryl electrophile. Biocompatible ammonium sulfate significantly enhances the reaction rate without influencing the site-specificity of π-clamp mediated arylation, enabling the fast synthesis of two site-specific antibody–drug conjugates that selectively kill HER2-positive breast cancer cells. Computational and structure–reactivity studies indicate that salts may tune the reaction rate through modulating the interactions between the π-clamp hydrophobic side chains and the electrophile. On the basis of this understanding, the salt effect is extended to other bioconjugation chemistry, and a new regioselective alkylation reaction at π-clamp cysteine is developed