Unstable Clusters Research Articles

The role of hydrolysis in biological effects of molybdenum cluster with DMSO ligands.

Biological applications of octahedral molybdenum cluster complexes are complicated by their hydrolytic instability, since hydrolysis leads to irreversible changes in the structure and properties of these compounds. On the other hand, if such changes are thoroughly investigated and understood, the hydrolysis process can become an important tool for regulating specific biological effects of the clusters. In this work, we demonstrate how the luminescence and biological properties (cellular uptake, cytotoxicity in the dark and photodynamic effect) of highly unstable cluster complex [{Mo6I8}(DMSO)6](NO3)4 change along with the degree of hydrolysis. Particularly, cluster solution preliminarily aged in water demonstrated lower dark and higher photoinduced cytotoxicity and higher cellular uptake in comparison with fresh solution.

Precursor nuclei on the bottom of a vibrating container: The onset of granular self-assembly crystallization

Kinetic energy is transferred through collisions to the millimeter particles that are in contact with the base of a vertically vibrated 3D container. In the early stages of a vibrational annealing process where the dimensionless acceleration is kept constant, the spontaneous appearance and disappearance of unstable clusters of ordered particles near the bottom surface of the container is observed. In later stages of this vibrational annealing process, the precursor nuclei stabilize becoming stable crystal seeds which resembles a thermal phase transition. Molecular Dynamics simulations based on these experimental observations are used to study the unstable–stable transition. The Ornstein–Zernike equation using the Percus–Yevick closure is applied to the stages before and after the observation of the stable crystal seeds in order to extract the effective potentials associated with the phase transition. Both the radial distribution function and the effective potentials show a clear correspondence of the spatial correlation as the crystallization phase begins to appear.

Characterization of structure evolution of Ti–O clusters in molten iron

The interaction of Ti–O clusters with one another and with the surrounding steel melt results in changes in size and shape, which affect strength and hardness in the finished steel. We used MD simulation with two parameters that, together, describe the structure evolution of Ti–O clusters. These are: (1) the radius of pair gyration , which reflects the degree of the compactness of the cluster, and (2) the radial distribution function, which identifies the type of titanium oxide. The value, which is inversely related to compactness, increases with the growth of clusters, then decreases abruptly when transformation occurs. Once the clusters form a particular TiO x , the value remains stable until next transformation. The growth of Ti–O clusters in molten iron is divided into three stages: unstable clusters → amorphous TiO structure → amorphous Ti3O5 structure. The mean critical size for the formation of amorphous TiO structure is about 7.0 Å × 9.6 Å × 21.6 Å. The critical size for the transformation of amorphous Ti3O5 structure is about 8.4 Å × 11.0 Å × 36.0 Å.

Lithium causes differential effects on postsynaptic stability in normal and denervated neuromuscular synapses

Lithium chloride has been widely used as a therapeutic mood stabilizer. Although cumulative evidence suggests that lithium plays modulatory effects on postsynaptic receptors, the underlying mechanism by which lithium regulates synaptic transmission has not been fully elucidated. In this work, by using the advantageous neuromuscular synapse, we evaluated the effect of lithium on the stability of postsynaptic nicotinic acetylcholine receptors (nAChRs) in vivo. We found that in normally innervated neuromuscular synapses, lithium chloride significantly decreased the turnover of nAChRs by reducing their internalization. A similar response was observed in CHO-K1/A5 cells expressing the adult muscle-type nAChRs. Strikingly, in denervated neuromuscular synapses, lithium led to enhanced nAChR turnover and density by increasing the incorporation of new nAChRs. Lithium also potentiated the formation of unstable nAChR clusters in non-synaptic regions of denervated muscle fibres. We found that denervation-dependent re-expression of the foetal nAChR γ-subunit was not altered by lithium. However, while denervation inhibits the distribution of β-catenin within endplates, lithium-treated fibres retain β-catenin staining in specific foci of the synaptic region. Collectively, our data reveal that lithium treatment differentially affects the stability of postsynaptic receptors in normal and denervated neuromuscular synapses in vivo, thus providing novel insights into the regulatory effects of lithium on synaptic organization and extending its potential therapeutic use in conditions affecting the peripheral nervous system.

Longitudinal typing of molecular HIV clusters in a statewide epidemic.

HIV molecular epidemiology is increasingly integrated into public health prevention. We conducted cluster typing to enhance characterization of a densely sampled statewide epidemic towards informing public health. We identified HIV clusters, categorized them into types, and evaluated their dynamics between 2004 and 2019 in Rhode Island. We grouped sequences by diagnosis year, assessed cluster changes between paired phylogenies, t0 and t1, representing adjacent years and categorized clusters as stable (cluster in t0 phylogeny = cluster in t1 phylogeny) or unstable (cluster in t0 ≠ cluster in t1). Unstable clusters were further categorized as emerging (t1 phylogeny only) or growing (larger in t1 phylogeny). We determined proportions of each cluster type, of individuals in each cluster type, and of newly diagnosed individuals in each cluster type, and assessed trends over time. A total of 1727 individuals with available HIV-1 subtype B pol sequences were diagnosed in Rhode Island by 2019. Over time, stable clusters and individuals in them dominated the epidemic, increasing over time, with reciprocally decreasing unstable clusters and individuals in them. Conversely, proportions of newly diagnosed individuals in unstable clusters significantly increased. Within unstable clusters, proportions of emerging clusters and of individuals in them declined; whereas proportions of newly diagnosed individuals in growing clusters significantly increased over time. Distinct molecular cluster types were identified in the Rhode Island epidemic. Cluster dynamics demonstrated increasing stable and decreasing unstable clusters driven by growing, rather than emerging clusters, suggesting consistent in-state transmission networks. Cluster typing could inform public health beyond conventional approaches and direct interventions.

Hidden Markov Model Segmentation to Demarcate Trajectories of Residual Apnoea-Hypopnoea Index in CPAP-Treated Sleep Apnoea Patients: The New Concept of a Telemonitogram

Background: Continuous positive airway pressure (CPAP), the reference treatment for obstructive sleep apnoea (OSA), is used by millions of individuals worldwide with remote telemonitoring providing daily information on CPAP usage and efficacy, a currently underused resource. Here, we aimed to implement state-of-the-art data science methods to describe heterogeneity and diversity of time-series of residual apnoea-hypopnoea indexes (rAHI) from CPAP telemonitoring. Methods: We analysed a CPAP telemonitoring database to model and cluster rAHI trajectories. Our primary objective was to use Hidden Markov models (HMMs) as a probabilistic model-based approach to extract features from rAHI time-series. Secondary goals were to identify clusters of rAHI trajectories and their relation to CPAP treatment outcomes, adherence and leaks. Findings: From telemonitoring records of 2,860 CPAP-treated patients (age: 66·31 ± 12·92 years, 69·9% male), HMM modelling revealed three states differing in variability within a given state and probability of shifting from one state to another. Six clusters of rAHI trajectories were identified ranging from well controlled CPAP-treated patients (Cluster 0: 669 (23%); mean rAHI 0·58 ± 0·59 events/hour) to the most unstable (Cluster 5: 470 (16%); mean rAHI 9·62 ± 5·62 events/hour). CPAP adherence was 30 minutes higher in cluster 0 compared to clusters 4 and 5 (p-value <0·01). Leaks were significantly more frequent in cluster 5. Interpretation: This new approach based on HMM might constitute the backbone for deployment of digital health solutions improving the interpretation of telemonitoring data from CPAP-treated patients. Funding Information: JLP, SB, and RT are supported by the French National Research Agency in the framework of the Investissements d’avenir” program (ANR-15-IDEX-02) and the “e-health and integrated care and trajectories medicine and MIAI artificial intelligence” Chairs of excellence from the Grenoble Alpes University Foundation (ANR-19-P3IA-0003). AM is supported by Probayes and MIAI in the framework of a “Convention Industrielle de Formation par la Recherche” (CIFRE) PhD. The PhD is also supported by the French National Research Agency (grant 2020/0007). Declaration of Interests: JLP reports grants from Air Liquide Foundation, grants and personal fees from Agiradom, grants and personal fees from AstraZeneca, grants from Fisher and Paykel, grants from Mutualia, grants and personal fees from Philips, grants and personal fees from Resmed, grants from Vitalaire, grants from Boehringer Ingelheim, grants from Jazz Pharmaceuticals, grants from Night Balance, grants from Sefam, outside the submitted work; JCB is employee of AGiR-a-dom, a French home-care provider; RT reports other from AGiR-a-dom, grants from Resmed, outside the submitted work; AM, RLH and MCS report other from AGiR-a-dom, and SB have no conflict of interest directly related to this work. Ethics Approval Statement: We analysed a CPAP telemonitoring database [registered and ethically approved by the French C.C.T.I.R.S: N°15.925bis and ethics regulations MR003 N° 1996650v0] to model and cluster patients’ rAHI trajectories.

High energy efficient lifetime management system and trust management framework for manet using self-configurable cluster mechanism

The maximum hard side of Mobile Ad Hoc Network (MANET) is that they are power resource-limited wherein energy cannot be replenished. Our evaluation intention is to give a high power saving management system for MANET. Cluster approaches in MANET make other nodes into small disjoint groups, wherever every cluster node encompasses an organizer known as Cluster Head (CH). The primary difficult task within the methods is retaining created clusters. To decide any node as Cluster Head, it is essential to summarize its constraints and eligibility, supported by the information of the node’s properties like its remaining power or energy. There may be a possibility of the Cluster Heads might be unsuccessful and act wrongly due to power instability. During failure, the Cluster Heads are unable to collect the data and transfer information well. This influences the effectiveness of the MANET. We can decrease the information failure by detecting CH’s failure earlier, and it needs the lowest improvement efforts. A self-configurable cluster mechanism is proposed. We planned to identify the unstable Cluster Heads, and soon it will be replaced by some other nodes. k-means protocol method has been developed to select Cluster Heads effectively. This protocol (k-means) operates on an interval or periodic irregular rotations of the Cluster Heads, and some of the clusters vary between 0 and 1. If the arbitrary number is smaller than the pre-decided preset (threshold) value, the node becomes a Cluster Heads for the existing round. We have achieved and realized a decrease in power and energy loss in comparison to other protocols like transmission and direct communication protocols. The experimental result suggests that the proposed scheme works appropriately to reduce energy dissipation compared to other protocols like transmission and direct communication protocols.

Nanocluster formation and two-step aging behavior in Al–Mg–Si(-xCu: X = 0–4 mass%) alloys

The effects of Cu addition on the clustering and two-step aging behavior in Al–Mg–Si(-Cu) alloys were analyzed by differential scanning calorimetry (DSC), the Vickers hardness and tensile tests, the three dimension atom probe (3DAP) and the transmission electron microscope (TEM). A high amount of Cu up to 4 mass % was added to the Al–Mg–Si alloys. Several types of clusters, namely, Cu–Mg, Cu–Si, Cu–Cu and Mg–Si–Cu, after natural aging for 2419.2 ks were formed in the Al–Mg–Si–Cu alloys. The size distribution and chemical composition of the clusters were characterized using 3DAP based on the maximum separation method. The cluster formation was promoted by 1Cu addition, but it was suppressed by 2Cu and 4Cu additions based on the analyses of cluster formation temperature and activation energy. Thermally unstable clusters were confirmed at the early stage of two-step aging at 170 °C after natural aging for 2419.2 ks. The amount of thermally unstable clusters was increased based on the hardness results. The peak hardness during single aging at 170 °C increased with an increasing Cu content. The negative and positive effect of two-step aging at 170 °C after natural aging for 2419.2 ks was clarified in Al–Mg–Si and Al–Mg–Si–Cu alloys, respectively. The formation temperature, activation energy, cluster size, and hardness changes with the cluster formation during natural aging and dissolution of cluster and precipitate formation during two-step aging at 170 °C are quantitatively described and those behaviors are discussed based on the age-hardening phenomena.

Synthesis and Characterization of the Highly Unstable Metalloid Cluster Ag64 (Pn Bu3 )16 Cl6.

The reduction of (nBu3P)AgCl with LiBH(sBu)3 in toluene gives the metalloid silver cluster Ag64(PnBu3)16Cl6 (1) as dark red, temperature‐ and light‐sensitive single crystals in high yield. 1 is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. The silver atoms in 1 show an overall brick‐shape arrangement, where structural resemblance to the close‐packed fcc and hcp structures is realized. Within 1 a 58 electron closed shell system is present. The light sensitivity renders 1 as a model compound for the primary seeds of the photo process, whereby this sensitivity, together with the high‐yield synthesis show that 1 is a perfect starting compound for further investigations like silver‐plating processes.

Crystallographic Characterization of Ti2C2@D3h(5)-C78, Ti2C2@C3v(8)-C82, and Ti2C2@Cs(6)-C82: Identification of Unsupported Ti2C2 Cluster with Cage-Dependent Configurations.

Fullerene cages are ideal hosts to encapsulate otherwise unstable metallic clusters to form endohedral metallofullerenes (EMFs). Herein, a novel Ti2C2 cluster with two titanium atoms bridged by a C2-unit has been stabilized by three different fullerene cages to form Ti2C2@D3h(5)-C78, Ti2C2@C3v(8)-C82, and Ti2C2@Cs(6)-C82, representing the first examples of unsupported titanium carbide clusters. Crystallographic results show that the configuration of the Ti2C2 cluster changes upon cage variation. In detail, the Ti2C2 cluster adopts a butterfly shape in Ti2C2@C3v(8)-C82 and Ti2C2@Cs(6)-C82 with Ti-C2-Ti dihedral angles of 156.35 and 147.52° and Ti-Ti distances of 3.633 and 3.860 Å, respectively. In sharp contrast, a stretched planar geometry of Ti2C2 is observed in Ti2C2@D3h(5)-C78, where a Ti-C2-Ti angle of 176.87° and a long Ti-Ti distance of 5.000 Å are presented. Consistently, theoretical calculations reveal that the cluster configuration is very sensitive to the cage shape which eventually determines the electronic structures of the hybrid EMF-molecules, thus adding new insights into modern coordination chemistry.

Novel atomic-scale mechanism of incipient plasticity in a chemically complex CrCoNi medium-entropy alloy associated with inhomogeneity in local chemical environment

Understanding the incipient plastic mechanism in metals is critical for their associated mechanical properties. While heterogeneous dislocation nucleation from pre-existing defects constitutes the most prevalent onset mechanism of plasticity in the conventional solutions, such a scenario may break down in the recently emerging chemically-disordered high/medium entropy alloys (HEAs/MEAs), owing to their unique multiple-component feature and the inevitable inhomogeneity in local atomic environments. Here, classical molecular dynamics simulations and first-principles density functional theory calculations are carried out to study the atomic-scale mechanisms governing the incipient plasticity in a prototypical chemically complex face-centered cubic (fcc) CrCoNi MEA. Dislocation nucleation is found to occur preferentially at an energetically unstable defect cluster with body-centered cubic like (bcc-like) atomic environment as a precursor, after certain deformation before plasticity, which is in contrast with the usual mechanism of heterogeneous dislocation nucleation in the conventional solute solution metals. The minimum energy pathway of dislocation nucleation from a bcc precursor is discussed to rationalize the usual phenomenon. First-principles athermal quasi-static compression test validates the mechanism suggested by atomistic simulations. Further electronic structure analysis suggests that the local bcc-like defect cluster is related to the localized electronic behaviors of Cr atoms and the weak Cr-Cr bonding, which promote the dislocation nucleation and therefore the incipient plasticity of CrCoNi MEA. The atomic and electronic insights reported here highlight the significant role of local chemical order in determining the mechanical property, and shed light on the strategy of optimizing mechanical performance via tailoring composition and local atomic arrangement in the generic highly concentrated solutions.

Italian Visual Cultures

ABSTRACT This article explores how ‘Visual Culture Studies’ has emerged since the 1990s as a productively unstable cluster of research concerns and practices, extending beyond the sectorial bounds of traditional visually-oriented disciplines such as art history or architecture. The two areas of screen studies and photography are explored as case studies that demonstrate how Visual Cultures approaches have expanded research horizons and enhanced teaching and outreach practice in Italian Studies. The article highlights aspects of visual production that have been variously dominant or marginalised in Italian Studies to date and explores how the new, interdisciplinary field fosters interconnections and exchanges, opens up discussion of the complexity of cultural production and media, and is enriched by engagement with visual, textual, and media theory.

Evolution of defects with isochronal annealing in helium-irradiated 316L studied by slow positron beam

The evolution of defects with isochronal annealing between 373 and 1273 K in 316L stainless steels, irradiated by helium ions at room temperature (RT), has been studied by the slow positron Doppler broadening spectroscopy (DBS). The results showed that with annealing temperature between RT and 673 K, the S parameters of sample were maintained. It indicates that below 673 K, on the one hand, some vacancies introduced by irradiation were gathered to form vacancy clusters and on the other hand, some vacancies migrated and recovered. From 773 K to 1073 K, there was continuous growth of HenVm cluster, resulting in rapid increasing of S parameter. After 1073 K, unstable HenVm clusters dissociated into vacancies and He atoms. The vacancies were vanished rapidly, which decreases the concentration of vacancy defects, leading to decline of S parameter.

In Situ Generation of the Cu@3D-ZrOx Framework Catalyst for Selective Methanol Synthesis from CO2/H2

Cu-based catalysts have been widely studied for direct hydrogenation of CO2 to methanol. Their activities quite depend on the amount of exposed active sites (e.g., Cu-oxide interfaces), which can be tuned by the particle size as well as porosity. Here, we report an active, selective, and stable Cu@ZrOx catalyst with a three-dimensional (3D) porous framework structure via the in situ reconstruction of size-confined Cu@UiO-66. The optimized CU-0.5-300 catalyst shows a high methanol selectivity of 78.8% at a conversion of 13.1% at 260 °C, 4.5 MPa, giving a methanol space-time yield of 796 g·kgcat–1·h–1. It also shows long-term stability for 105 h in a time-on-stream test. Such good performance benefits from abundant Cu–ZrOx interfaces and a stable 3D ZrOx framework. During the reaction, ZrOx species in situ evolves from the unstable Zr-oxide cluster (the building unit of UiO-66) or amorphous ZrO2 to a stable tetragonal ZrO2 phase, but strong metal–support interaction (SMSI) at Cu–ZrOx interfaces retains. The...

Prediction of a multi-hazard chain by an integrated numerical simulation approach: the Baige landslide, Jinsha River, China

Successive major landslides during October and November 2018 in Baige village, eastern Tibet, dammed the Jinsha River on two occasions, and the subsequent dam breaches instigated a multi-hazard chain that flooded many towns downstream. Analysis of high-resolution aerial images and field investigations unveiled three potentially unstable rock mass clusters in the source area of the landslides, suggesting possible future failures with potential for river-damming and flooding. In order to evaluate and understand the disaster chain effect linked to the potentially unstable rock mass, we systematically studied the multi-hazard scenarios through an integrated numerical modelling approach. Our model begins with an evaluation of the probability of landslide failure, including runout and river damming, and then addresses the dam breach and resultant flood—hence simulating and visualising an entire disaster chain. The model parameters were calibrated using empirical data from the two Baige landslides. Then, we predict the future cascading hazards via seven scenarios according to all possible combinations of potential rock mass failure. For each scenario, the landslide runouts, dam-breaching, and flooding are numerically simulated with full consideration of uncertainties among the model input parameters. The maximum dam breach flood extent, depth, velocity, and peak arrival time are predicted at sequential sites downstream. As a first attempt to simulate the full spectrum of a landslide-induced multi-hazard chain, our study provides insights and substantiates the value provided by multi-hazard modelling. The integrated approach described here can be applied to similar landslide-induced chains of hazards in other regions.

Stability and bonding nature for icosahedral or planar cluster of hydrogenated boron or aluminum

Ab initio molecular orbital calculations are performed for B13−, Al13−, B12H122−, Al12H122−, Si10, and Si10H16 clusters. The highest occupied molecular orbital (HOMO) of stable and unstable clusters is bonding and antibonding orbitals, respectively. The cluster size dependences of the orbital energies are almost the same for B13− and Al13− icosahedral clusters, when the size and the energy are properly normalized. The normalized factors for size and energy are almost coincident with the ratios of those of the atomic outer s orbitals. On the other hand, the most stable size of B13− is smaller than that of Al13−, and this ratio of the stable size seems to be affected by the ratio of the sizes of the atomic outer p orbitals. As a result, B13− and Al13− icosahedral clusters have antibonding and bonding orbitals for HOMOs and so are unstable and stable, respectively. The situation for B13− and Al13− planar clusters is opposite to that discussed above for the icosahedral clusters. The orbital energies for the metallic bonding Al13− icosahedral and Si10 clusters can be reproduced by the Woods–Saxon model; however, those for the unstable B13− icosahedral and covalent bonding B12H122−, Al12H122−, and Si10H16 clusters cannot be reproduced by the Woods–Saxon model. After optimization of the parameters of the Woods–Saxon model for the Al13− icosahedral and Si10 clusters, the orbital energies are reproduced very well and the sizes and shapes of the potential are reasonable.

Characterization of GnRH Pulse generator activity in male mice using GCaMP fiber photometry

Kisspeptin neurons located in the hypothalamic arcuate nucleus are thought to represent the GnRH pulse generator responsible for driving pulsatile LH secretion. The recent development of GCaMP6 fiber photometry technology has made it possible to perform long-term recordings of the population activity of the arcuate nucleus kisspeptin (ARNKISS) neurons in conscious-behaving mice. Using this approach, we show that ARNKISS neurons in intact male mice exhibit episodes of synchronized activity that last ∼2 minutes and have a mean inter-episode interval of 166 minutes, with a very wide range (43 to 347 minutes). Gonadectomy resulted in dramatic changes in the dynamics of ARNKISS neuron behavior with temporally distinct alterations in synchronization episode (SE) amplitude (sevenfold increase), inter-SE frequency (range, 2 to 58 minutes), and duration (up to 28 minutes), including the frequent appearance of seemingly unstable clusters of doublet and triplet SEs. The combination of photometry with repeated blood sampling revealed a perfect correlation between ARNKISS neuron population SEs and LH pulses in intact and short-term gonadectomized (GDX) mice. No differences were detected in SE frequency across 24 hours in either intact or GDX mice. These observations further support a role for ARNKISS neurons as the GnRH pulse generator and show that it operates in a stochastic manner without diurnal variation in both intact and GDX male mice. The removal of gonadal steroids has multiple time-dependent effects upon ARNKISS neuron synchronizations, indicating their critical role in shaping pulse generator behavior.

Light-Induced Size-Growth of Atomically Precise Nanoclusters.

A photo-induced transformation from [Au23(S-c-C6)16]-(TOA)+ to Au28(S-c-C6)20 nanocluster was first reported in this work. The [Au23(S-c-C6)16]-(TOA)+ nanocluster is first excited to [Au23(S-c-C6)16]•-(TOA)+ by photons with energy higher than its Eg (Eg = HOMO - LUMO energy gap), and then, the negatively charged [Au23(S-c-C6)16]•- nanocluster was oxidized to the neutral state by transfering one electron to O2. The unstable neutral cluster [Au23(S-c-C6)16]0 obtained was decomposed into smaller nanocluster and finally reassembled into the Au28(S-c-C6)20 nanocluster. Time-dependent UV-vis, matrix-assisted laser desorption/ionization time of flight mass spectrometry, electron paramagnetic resonance, and electrospray ionization mass spectrometry characterizations were performed to monitor the nanocluster size transformation.

Food security in selected Middle East and North Africa (MENA) countries: an inter-country comparison

This study aims to assess and compare food security and its socio-demographic correlates in 18 Middle East and North African (MENA) countries that fall under the auspices of the World Health Organization Regional Office of the Eastern Mediterranean (EMRO). This cross-sectional study is based on data from the 2016 Gallup World Poll. The study sample included an average of 1000 individuals per country (n = 18,079). Food security status of individuals was measured using the Food Insecurity Experience Scale (FIES). Various statistical analyses such as descriptive, bivariate, and binary logistic regression were conducted. Countries were categorized into three clusters based on frequency of moderate to severe food insecurity, as well as political stability index and per capita income. The frequency of severe food insecurity was significantly lower in countries in cluster 1 (rich, stable) (5.0%) compared to the second (middle-low income, less stable) (13.6%), and third (middle-low income, unstable) (26.7%) clusters (P < 0.001). Based on logistic regression analyses, income quintile per capita, personal health index and education levels were the main predictors of food insecurity in all three clusters. The results provide insight into the diversity of the MENA countries studied and the different policy options needed to improve their food security.

Full distribution of clusters with universal couplings and in-medium effects

Light and heavy clusters are calculated for asymmetric warm nuclear matter in a relativistic mean-field approach. In-medium effects, introduced via a universal cluster-meson coupling, and a binding energy shift contribution, calculated in a Thomas-Fermi approximation, were taken into account. This work considers, besides the standard lightest bound clusters $^4$He, $^3$He, $^3$H, and $^2$H, also stable and unstable clusters with higher number of nucleons, in the range $5\leq A \leq 12$, as it is natural that heavier clusters also form in core-collapse supernova matter, before the pasta phases set in. We show that these extra degrees of freedom contribute with non-negligible mass fractions to the composition of nuclear matter, and may prevail over deuterons and $\alpha$ particles at high density in strongly asymmetric matter, and not too high temperatures. The presence of the light clusters reduces the contribution of heavy clusters to a much smaller density range, and to a smaller mass fraction.