Terminal Complex Research Articles

5-adenosine monophosphate promotes signal adaptation in PKA signaling.

Protein Kinase A (PKA) plays a central role in several cellular processes and its activity is tightly regulated by 2nd messenger 3,5-cyclic adenosine monophosphate (cAMP)-signaling. While the role of cAMP in PKA activation is well established, the significance of its hydrolysis end-product, 5-adenosine monophosphate (AMP) is poorly understood. AMP is generated upon hydrolysis of cAMP bound to the PKA regulatory subunits (RIα) catalyzed by phosphodiesterases. All components of the cAMP-PKA signaling pathway that include PDEs are compartmentalized into signalosomal units. Our research has shown that PDEs in proximity with PKA RIα in signalosomes lead to formation of a signal termination complex of PDEs and RIα, that facilitates cAMP substrate channeling from the PKA binding site to the PDE catalytic site. In contrast to the long held view that AMP diffused away from the PKA signalosome following cAMP hydrolysis, AMP is a regulatory end-product of each round of PKA activation and termination. Here we report high resolution structures of the AMP bound conformations of RIα and PDE8A catalytic domain (PDE8c) by cryo-EM. We have further captured AMP-bound end-state signal termination complex of PDE8c with RIα, by orthogonal electron microscopy screening, amide hydrogen/deuterium exchange mass spectrometry. Our results describe an undiscovered active role of AMP in signal termination and adaptation in PKA signaling.

Structural basis for intrinsic transcription termination.

Efficient and accurate termination is required for gene transcription in all living organisms1,2. Cellular RNA polymerases in both bacteria and eukaryotes can terminate their transcription through a factor-independent termination pathway3,4-called intrinsic termination transcription in bacteria-in which RNA polymerase recognizes terminator sequences, stops nucleotide addition and releases nascent RNA spontaneously. Here we report a set of single-particle cryo-electron microscopy structures of Escherichia coli transcription intrinsic termination complexes representing key intermediate states of the event. The structures show how RNA polymerase pauses at terminator sequences, how the terminator RNA hairpin folds inside RNA polymerase, and how RNA polymerase rewinds the transcription bubble to release RNA and then DNA. These macromolecular snapshots define a structural mechanism for bacterial intrinsic termination and a pathway for RNA release and DNA collapse that isrelevant for factor-independent termination by all RNA polymerases.

Dehydrogenation reaction of triethylamine by an electrophilic terminal phosphinidene complex.

Reaction of a transiently formed terminal phosphinidene complex with triethylamine resulted in the formation of an sp3 C-H insertion product, as revealed by 31P NMR spectroscopy, which was isolated as semi-solid compound. However, if the reaction was continued for 24 h, a primary phosphane complex was obtained eventually. The compounds were characterised by NMR spectroscopy and mass spectrometry. Formation of the final products is explained by a mechanistic proposal based on DFT calculations.

Joint Trajectory Plan and Resource Allocation for UAV-Enabled C-NOMA in Air-Ground Integrated 6 G Heterogeneous Network

Leveraging unmanned aerial vehicles (UAVs) for access and high altitude platform stations (HAPSs) for data backhaul to construct the Air-Ground Integrated Network (AGIN), is a feasible solution to achieve seamless network coverage for remote IoT devices in future 6 G era. However, since the number of terminals increases exponentially, it is essential to improve spectrum efficiency and throughput of the system. In addition, the limited on-board energy storage of UAVs and finite battery of IoT terminals make the system energy efficiency (EE) a new concern. To cope with the above mentioned challenges, in this study we first put forward a clustered-NOMA (C-NOMA)-enabled heterogeneous AGIN model for remote areas including one HAPS for backhaul and multiple UAVs for access, where C-NOMA is used to obtain both improved system throughput and terminal complexity. Then, we study the joint UAV trajectory plan and resource allocation problem in order to maximize the system EE. Since it is a mixed integer nonlinear programming (MINLP) issue coupled with transmission power, subchannel allocation, UAV trajectory and speed control, this problem is decoupled into two subproblems and solved iteratively. For the first one, the optimal channel and power strategy is obtained by our subchannel allocation and power control for AGIN EE (SAPAE) maximum algorithm according to Lagrange dual decomposition method. For the second, for transforming the nonconvex problem into a convex one, we provide the successive convex approximation-based UAV trajectory and speed optimization for AGIN EE (SUTSAE) maximum algorithm, and then the near-optimal UAV trajectory and flight speed are obtained. We conduct extensive experiments to compare with other benchmark methods. It is shown that the proposed approach is better in EE and spectrum efficiency.

Microbial influence in the Messinian sedimentation: Example of Cap Bon (NE Tunisia)

Messinian sedimentation in Tunisia is characterized by the absence of large carbonate platforms known in many Mediterranean marginal basins. As a result, correlations are not easy to establish in order to integrate it into a general pattern of development at the regional level. However, the discovery of microbial constructions of metric scale makes it possible to precise uncertain points. Thus in the sector of Cap Bon in the northeast of Tunisia, stromatolitic constructions can form, over distances of several hundred meters, domes containing columnar structures at different scales as well as carbonate beds showing sedimentary ripples also of microbialite nature. The highlighting of an assemblage of microbialites, associated with oolitic deposits, allows linking these formations to the Terminal Carbonate Complex which finds its place at a part of the so-called Messinian Salinity Crisis.

Progress in the chemistry of molecular actinide-nitride compounds.

The chemistry of actinide-nitrides has witnessed significant advances in the last ten years with a large focus on uranium and a few breakthroughs with thorium. Following the early discovery of the first terminal and bridging nitride complexes, various synthetic routes to uranium nitrides have since been identified, although the range of ligands capable of stabilizing uranium nitrides still remains scarce. In particular, both terminal- and bridging-nitrides possess attractive advantages for potential reactivity, especially in light of the recent development of uranium complexes for dinitrogen reduction and functionalization. The first molecular thorium bridged-nitride complexes have also been recently identified, anticipating the possibility of expanding nitride chemistry not only to low-valent thorium, but also to the transuranic elements.

Variable temperature kinetic isotope effects demonstrate extensive tunnelling in the C-H activation reactivity of a transition metal-oxo complex.

There has been recent interest about how the rates of concerted proton electron transfer (CPET) are affected by the thermodynamic parameters of intermediates from stepwise PT or ET reactions. Semiclassical arguments have been used to explain these trends despite the importance of quantum mechanical tunneling in CPET reactions. Here we report variable temperature kinetic isotope effect (KIE) data for the reactivity of a terminal Co-oxo complex with C-H bonds. The KIEs for the oxidation of both 9,10-dihydroanthracene (DHA) and fluorene have significant tunneling contributions and fluorene has a largely temperature-insensitive KIE which is inconsistent with semiclassical models. These findings support recent calls for a more detailed understanding of tunneling effects in thermodynamically imbalanced CPET reactions.

PGC-1α senses the CBC of pre-mRNA to dictate the fate of promoter-proximally paused RNAPII

PGC-1α is well established as a metazoan transcriptional coactivator of cellular adaptation in response to stress. However, the mechanisms by which PGC-1α activates gene transcription are incompletely understood. Here, we report that PGC-1α serves as a scaffold protein that physically and functionally connects the DNA-binding protein estrogen-related receptor α (ERRα), cap-binding protein 80 (CBP80), and Mediator to overcome promoter-proximal pausing of RNAPII and transcriptionally activate stress-response genes. We show that PGC-1α promotes pausing release in a two-arm mechanism (1) by recruiting the positive transcription elongation factor b (P-TEFb) and (2) by outcompeting the premature transcription termination complex Integrator. Using mice homozygous for five amino acid changes in the CBP80-binding motif (CBM) of PGC-1α that destroy CBM function, we show that efficient differentiation of primary myoblasts to myofibers and timely skeletal muscle regeneration after injury require PGC-1α binding to CBP80. Our findings reveal how PGC-1α activates stress-response gene transcription in a previously unanticipated pre-mRNA quality-control pathway.

Pulkovo Airport Terminal in Leningrad is a Masterpiece of Domestic Modernism

This article is devoted to the Pulkovo airport terminal complex in Leningrad – Saint-Petersburg. The article offers comprehensive research on the architectural project (the project leader A.V. Zhuk) and its implementation as an architectural phenomenon in a sociocultural context. The research methodology is based on historical, chronological, structural, functional, and semiotic approaches. Based on historical and cultural analysis of the transformation and improvement of the project during the period of its realisation, the article shows a few innovative functions of the airport, besides its primary technological function, such as: representative function; memorial function, preserving results of the creative team's work and builders work; artistic function within the ensemble perception of the project. The article also shows the project's dynamic of development and enhancement throughout fulfilled work on it. The article illustrates the design solutions embodied in full in the construction, reflects the scale of construction and improvement of professional methods and techniques. The author also reviewed and analysed texts and documents contemporary to the architectural conception and its implementation. Based on the research, the author makes a conclusion about the Pulkovo airport being an object, perfect by its function and artistic image, representing a synthesis of innovative methods, taking landscape features into account, and translating the author's cultural experience. The relevance of the preservation of the airport is related to its characteristics, which are unique for world architecture and Saint-Petersburg's environment. The scientific novelty of the research lies in the statement about the building of Pulkovo airport being a perfect example of an embodiment of rationalism ideas in conjunction with the creation of vivid artistic imagery. Also, the thesis is presented, about the creative team successfully combining bold technological innovations with a humanistic focus of the functional object.

From Divalent to Pentavalent Iron Imido Complexes and an Fe(V) Nitride via N-C Bond Cleavage.

As key intermediates in metal-catalyzed nitrogen-transfer chemistry, terminal imido complexes of iron have attracted significant attention for a long time. In search of versatile model compounds, the recently developed second-generation N-anchored tris-NHC chelating ligand tris-[2-(3-mesityl-imidazole-2-ylidene)-methyl]amine (TIMMNMes) was utilized to synthesize and compare two series of mid- to high-valent iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate en route to an isolable Fe(V) nitrido complex. The chemistry toward the iron adamantyl imides was achieved by reacting the Fe(I) precursor [(TIMMNMes)FeI(N2)]+ (1) with 1-adamantyl azide to yield the corresponding trivalent iron imide. Stepwise chemical reduction and oxidation lead to the isostructural series of low-spin [(TIMMNMes)Fe(NAd)]0,1+,2+,3+ (2Ad-5Ad) in oxidation states II to V. The Fe(V) imide [(TIMMNMes)Fe(NAd)]3+ (5Ad) is unstable under ambient conditions and converts to the air-stable nitride [(TIMMNMes)FeV(N)]2+ (6) via N-C bond cleavage. The stability of the pentavalent imide can be increased by derivatizing the nitride [(TIMMNMes)FeIV(N)]+ (7) with an ethyl group using the triethyloxonium salt Et3OPF6. This gives access to the analogous series of ethyl imides [(TIMMNMes)Fe(NEt)]0,1+,2+,3+ (2Et-5Et), including the stable Fe(V) ethyl imide. Iron imido complexes exist in a manifold of different electronic structures, ultimately controlling their diverse reactivities. Accordingly, these complexes were characterized by single-crystal X-ray diffraction analyses, SQUID magnetization, and electrochemical methods, as well as 57Fe Mössbauer, IR vibrational, UV/vis electronic absorption, multinuclear NMR, X-band EPR, and X-ray absorption spectroscopy. Our studies are complemented with quantum chemical calculations, thus providing further insight into the electronic structures of all complexes.

R-Type Fonticins Produced by Pragia fontium Form Large Pores with High Conductance.

Fonticins are phage tail-like bacteriocins produced by the Gram-negative bacterium Pragia fontium from the family Budviciaceae. This bacterium produces contractile-type particles that adsorb on the surface of sensitive bacteria and penetrate the cell wall, probably during contraction, in a way similar to the type VI secretion system. We characterized the pore-forming activity of fonticins using both living cells and in vitro model membranes. Using a potassium leakage assay, we show that fonticins are able to permeabilize sensitive cells. On black lipid membranes, single-pore conductance is about 0.78 nS in 1 M NaCl and appears to be linearly dependent on the increasing molar strength of NaCl solution, which is a property of considerably large pores. In agreement with these findings, fonticins are not ion selective for Na+, K+, and Cl-. Polyethylene glycol 3350 (PEG 3350) molecules of about 3.5 nm in diameter can enter the fonticin pore lumen, whereas the larger molecules cannot pass the pore. The size of fonticin pores was confirmed by transmission electron microscopy. The terminal membrane-piercing complex of the fonticin tube probably creates a selective barrier restricting passage of macromolecules. IMPORTANCE Phage tail-like bacteriocins are now the subject of research as potent antibacterial agents due to their narrow host specificity and single-hit mode of action. In this work, we focused on the structure and mode of action of fonticins. According to some theories, related particles were initially adapted for passage of double-stranded DNA (dsDNA) molecules, but fonticins changed their function during the evolution; they are able to form large pores through the bacterial envelope of Gram-negative bacteria. As various pore-forming proteins are extensively used for nanopore sequencing and stochastic sensing, we decided to investigate the pore-forming properties of fonticin protein complexes on artificial lipid membranes. Our research revealed remarkable structural properties of these particles that may have a potential application as a nanodevice.

Niobium Bis‐ and Mono(Pentafulvene) Complexes: E−H Bond Cleavage and Insertion Reactions (E=C, N, O)

AbstractBis(η5:η1‐(di‐para‐tolyl)pentafulvene)niobium chloride (1) reacts with methyl lithium via salt metathesis to the methylated bis(pentafulvene)niobium complex 2, and with lithium 2,6‐diisopropylanilide addition and subsequent N−H bond activation to the imido mono(pentafulvene)niobium complex 3. Avoiding the competing protonation of the chloride, bis(pentafulvene)niobium complex 2 reacts with primary aromatic and aliphatic amines to form terminal niobocene imido complexes, and with water to form the analog terminal oxo complex. Secondary methyl amines undergo a simultaneous N−H and C−H activation to form niobaaziridines under mild conditions. In contrast to other reported examples, 3 can be employed to investigate the uncontested reactivity of mono(pentafulvene)niobium complexes. Reaction with 4‐tert‐butylphenol selectively yields a niobocene phenolate complex. Unprecedented for mono(pentafulvene)niobium complexes, treating 3 with multiple‐bond‐containing substrates (nitriles, isocyanates) smoothly results the insertion into the Nb‐Cexo σ‐bond, forming the corresponding alkylidene amido and imidato complexes.

Preparation and Characterization of a Formally NiIV-Oxo Complex with a Triplet Ground State and Application in Oxidation Reactions.

High-valent first-row transition-metal-oxo complexes are important intermediates in biologically and chemically relevant oxidative transformations of organic molecules and in the water splitting reaction in (artificial) photosynthesis. While high-valent Fe- and Mn-oxo complexes have been characterized in detail, much less is known about their analogues with late transition metals. In this study, we present the synthesis and detailed characterization of a unique mononuclear terminal Ni-O complex. This compound, [Ni(TAML)(O)(OH)]3-, is characterized by an intense charge-transfer (CT) band around 730 nm and has an St = 1 ground state, as determined by magnetic circular dichroism spectroscopy. From extended X-ray absorption fine structure (EXAFS), the Ni-O bond distance is 1.84 Å. Ni K edge XAS data indicate that the complex contains a Ni(III) center, which results from an unusually large degree of Ni-O π-bond inversion, with one hole located on the oxo ligand. The complex is therefore best described as a low-spin Ni(III) complex (S = 1/2) with a bound oxyl (O•-) ligand (S = 1/2), where the spins of Ni and oxyl are ferromagnetically coupled, giving rise to the observed St = 1 ground state. This bonding description is roughly equivalent to the presence of a Ni-O single (σ) bond. Reactivity studies show that [Ni(TAML)(O)(OH)]3- is a strong oxidant capable of oxidizing thioanisole and styrene derivatives with large negative ρ values in the Hammett plot, indicating its electrophilic nature. The intermediate also shows high reactivity in C-H bond activation of hydrocarbons with a kinetic isotope effect of 7.0(3) in xanthene oxidation.

Metal-Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P).

Decarbonylation along with P-atom transfer from the phosphaethynolate anion, PCO- , to the NbIV complex [(PNP)NbCl2 (Nt BuAr)] (1) (PNP=N[2-Pi Pr2 -4-methylphenyl]2 - ; Ar=3,5-Me2 C6 H3 ) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(Nt BuAr)] (2). Reduction of 2 with CoCp*2 cleaves the P-P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(Nt BuAr)] (3). Theoretical studies have been used to understand both the coupling of the P-atom and the reductive cleavage of the P-P bond. Reaction of 3 with a two-electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P-P coupled ligand, namely [(PNPP)Nb=S(Nt BuAr)] (4).

Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

AbstractDecarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO−, to the NbIV complex [(PNP)NbCl2(NtBuAr)] (1) (PNP=N[2‐PiPr2‐4‐methylphenyl]2−; Ar=3,5‐Me2C6H3) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(NtBuAr)] (2). Reduction of 2 with CoCp*2 cleaves the P−P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(NtBuAr)] (3). Theoretical studies have been used to understand both the coupling of the P‐atom and the reductive cleavage of the P−P bond. Reaction of 3 with a two‐electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P−P coupled ligand, namely [(PNPP)Nb=S(NtBuAr)] (4).

Glacial history and depositional environments in little Storfjorden and Hambergbukta of Arctic Svalbard since the younger dryas

Geophysical and lithological data provide crucial information for the understanding of glacial history in Arctic Svalbard. In this study, we reconstructed the glacier-induced depositional environments of Little Storfjorden and its tributary, Hambergbukta, over the last 13 ka to better understand the glacial history of southeastern Svalbard. The combined uses of swath-bathymetry, high-resolution seismic stratigraphy, and multiple-proxy measurements of sediment cores allowed us to define five steps of glacier-induced depositional environments: 1) deposition of massive, semi-consolidated gravelly sandy mud (Facies 1) during re-advance or still-stand of the marine-based glaciers/ice streams in Little Storfjorden during Younger Dryas (13–12 ka); 2) deposition of massive mud to gravelly sandy mud (Facies 2A and B) during glacial retreat until the earliest Holocene (12–10.1 ka); 3) sediment winnowing by enhanced bottom currents during the early to middle Holocene (10.1–3.7 ka); 4) deposition of bioturbated sandy mud (Facies 3) with high productivity under seasonal sea ice conditions during the late Holocene (3.7–0.7 ka); and 5) deposition of (slightly) bioturbated sandy to gravelly mud (Facies 4) affected by glacier surges since Little Ice Age (LIA) (Facies 4). In addition to seismic stratigraphy, depositional patterns of IRD in Little Storfjorden indicate that the glacier surges in Hambergbukta occurred only after ∼0.7 ka. This suggests that the terminal moraine complex (TMC) represents the maximum extent of the LIA surges, which argues against the recent inference for the TMC formation during pre-LIA. This study shows the importance of multiple parameters to better understand the current behavior of tidewater glaciers in the Svalbard fjords in response to rapid climate change.

Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand.

We report the direct synthesis of the terminal pnictidenes [An(TrenTCHS )(PnH)][M(2,2,2-cryptand)] (TrenTCHS ={N(CH2 CH2 NSiCy3 )3 }3- ; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(TrenTCHS )(PnH2 )] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky TrenTCHS ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(TrenTIPS ){μ-As(H)K(15-crown-5)}] (TrenTIPS ={N(CH2 CH2 NSiPri 3 )3 }3- ) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the σ-bond changes little but the π-bond is significantly perturbed.

Actinide Pnictinidene Chemistry: A Terminal Thorium Parent‐Arsinidene Complex Stabilised by a Super‐Bulky Triamidoamine Ligand

AbstractWe report the direct synthesis of the terminal pnictidenes [An(TrenTCHS)(PnH)][M(2,2,2‐cryptand)] (TrenTCHS={N(CH2CH2NSiCy3)3}3−; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(TrenTCHS)(PnH2)] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super‐bulky TrenTCHS ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium‐arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(TrenTIPS){μ‐As(H)K(15‐crown‐5)}] (TrenTIPS={N(CH2CH2NSiPri3)3}3−) reveals a stronger Th−As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically‐bound K‐ion; the σ‐bond changes little but the π‐bond is significantly perturbed.

Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate

Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2C═NPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH⧧ and ΔS⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2C═NPh), including a single-crystal X-ray structure determination, was achieved.

P-017 A FRAMEWORK FOR MULTIDISCIPLINARY TEAM MANAGEMENT OF ABDOMINAL WALL RECONSTRUCTION

Abstract Aim Incisional hernias are common and can significantly impact a patient's quality of life. Traditionally, abdominal wall reconstruction (AWR) has been performed by general surgeons, or those with special interest, often working in isolation. However, there is increasing awareness of pre-optimisation, risk stratification, enhanced training, and personalising treatment using a wide range of techniques. Methods & Results For complex and higher-risk procedures, Multidisciplinary team (MDT) management is considered the standard of care for optimising outcomes. The lack of standardised protocols and clear evidence in AWR means that surgical management can vary greatly. This makes the MDT process even more important due to the complexity of the decision-making involved. We describe a successful MDT process for complex abdominal wall reconstruction at a tertiary referral centre. Patients are reviewed at weekly AWR meetings with a multidisciplinary team, which includes consultants, advanced clinical practitioners and trainees. This is an opportunity for objective risk stratification, radiological review and assessment of the patient's goals before preoptimization and operative planning. Prospective data is collected on all patients to allow for quality improvement and service development. Conclusion MDT management of abdominal wall hernia is gaining popularity but remains poorly established in most regions. The involvement of surgical colleagues and other specialists is crucial in developing this growing field of surgery. We hope to expand our team to include Radiologists and Nutritionists, with the possibility of extending to regional networks, as we continue to explore new techniques and methods in managing complex abdominal wall hernias.